Heterocycle-substituted alkyl diaryl phosphine rhodium caronyl hydride complex hydroformylation catalyst compositions

ABSTRACT

Compositions of matter are disclosed which are highly useful in hydroformylation processes. The compositions are non-charged, non-chelated bis- and tris-(alkyl diaryl phosphine) rhodium carbonyl hydrides. The substituents of the alkyl group include heteroorganic radicals containing silane, silicone, ether, ester, keto and hydroxy oxygen, phosphine oxide and phosphorus ester phosphorus, amine, amide, amine oxide and heterocyclic nitrogen groups. 
     These compositions are highly stable and selective catalysts for the hydroformylation of olefins under certain conditions. The disclosed catalyst systems contain a large excess of phosphine ligand and employ alpha-olefin plus synthesis gas reactant mixtures having a high H 2  /CO ratio at relatively low pressures. They produce mostly aldehydes derived from terminal attack on the alpha-olefin reactant. In the case of low olefins, such as butene-1, the products can be advantageously removed in a continuous manner, as distillate components from a ligand reaction mixture kept at an elevated temperature and continuously fed by an appropriate mixture of the reactants.

This division of application Ser. No. 374,548, filed 5/3/82, which is R.60 divisional of 120,971 filed 2/12/80.

TECHNICAL FIELD

The present invention is related to selective alkyl diaryl phosphinetransition metal complex olefin hydroformylation catalysts. Moreparticularly, the subject of this invention is certain, new selectivealkyl diaryl phosphine rhodium complex hydroformylation catalysts. Assuch, the invention is specifically related to substituted tris-(alkyldiphenyl phosphine) rhodium carbonyl hydride complexes.

A special aspect of the invention is concerned with the preparation,physicochemical and catalytic properties of the novel complexes, i.e.,phosphine basicity, stereochemistry versus complex formation, thermalstability of complexes, correlations of catalyst selectivity andactivity with hydroformylation reaction rates at different temperatures.The effects of excess phosphine ligand, excess hydrogen, carbon monoxidepartial pressure on the catalytic properties and on catalyst selectivityto linear aldehydes are also related.

BACKGROUND ART

Transition metal complexes containing phosphine ligands have been widelystudied as catalysts for hydroformylation and hydrogenation. Generalapplication of such complexes in reaction with carbon monoxide arediscussed, e.g., in the monograph of Juergen Falbe, "Carbon Monoxide inOrganic Synthesis, Springer Verlag, New York, 1970.

There were a number of all inclusive patent disclosures on the use ofphosphine rhodium complexes as hydroformylation catalysts: GermanOffenlegungsschrift 2,758,473 by W. E. Smith (assigned to GeneralElectric) disclosed them for allyl alcohol hydroformylation; U.S. Pat.No. 4,137,240 by M. L. Peterson (assigned to E. I. DuPont de Nemours andCo.) described them for 2-vinyl-4-methyl-1,3-dioxane batchhydroformylation; U.S. Pat. No. 3,965,192 by F. B. Booth (assigned toUnion Oil Co. of California) disclosed them for the hydroformylation ofmonoolefins; U.S. Pat. No. 4,041,082 by T. Onoda and T. Masuyama(assigned to Mitsubishi Chemical Industries) defined such complexesbroadly in a process for their reactivation; U.S. Pat. No. 3,821,311 byO. R. Hughes and M. E. D. Millman (assigned to Celanese Corp.) alsodisclosed the use of such complexes broadly when used with bases forcombined hydroformylation, aldolization. Similarly, British Pat. No.1,243,189 by M. J. Lawrenson and G. Foster (assigned to BritishPetroleum Co., Ltd.) provided an all inclusive definition of phosphinesin such catalyst complexes also containing chelating diketones. Finally,U.S. Pat. No. 4,052,461 by H. B. Tinker and D. E. Morris (assigned toMonsanto Co.) disclosed rhodium containing cations which can include anytertiary phosphine.

Most of the prior art work was carried out with either triaryl phosphineor trialkyl phosphine complexes. The present study concentrated on aninvestigation of the complexes of some "mixed ligand structures," i.e.,alkyl diphenyl phosphines. Prior to the present work, rhodium complexesof these ligands could not be used tp advantage.

The basic chemistry of hydroformylation and its catalysis by transitionmetal compounds, including phosphine-rhodium complexes is known and hasbeen recently reviewed and summarized by R. L. Pruett in Vol. 17 of"Advances in Organo Metallic Chemistry" ed. S. G. Stone and R. West,Academic Press, New York, N.Y. 1979 in a chapter entitledHydroformylation, Pruett concluded that, for a selective rhodiumcatalyzed hydroformylation of alpha-olefins to n-aldehydes, criticalcombinations of several reaction parameters were required. The authorstates that these parameters included low partial pressure of carbonmonoxide, high concentration of excess phosphite or aryl phosphineligands and low total gas pressure.

In U.S. Pat. Nos. 3,527,809 and 3,917,661; Pruett and Smith state thatsuitable ligands for rhodium catalysts for hydroformylation must beweakly basic, having a half neutralization potential (ΔHMP) of at least425 millivolts (preferably 500) above that of diphenyl guanidine. Assuch weakly basic ligands, Pruett and Smith mentioned among othersphosphites and triaryl phosphines. They specifically indicate thatstronger phosphines bases, such as diaryl alkyl phosphines, should beexcluded as ligands for selective rhodium catalysis. Similar disclosuresare also contained in Pruett and Smith's U.S. Pat. No. 4,148,830, wherethey additionally state that suitable ligands should be free ofsterically hindered aromatic groups.

In German Offenlegungsschrift 2,802,922 (based on U.S. Ser. No. 762,335,filed on Jan. 25, 1977 in the names of D. G. Morrell and P. D. Sherman,Jr.), there is described a process including the addition of smallamounts of diaryl alkyl phosphine ligands to a tris-triphenyl phosphinerhodium complex system. However, substantially all of the free ligand inthe Morrell et al. system is a triaryl ligand, and it is specificallystated that the invention is not intended to include the use of diarylalkyl phosphine ligands alone. Some of the diaryl alkyl phosphineligands which are apparently disclosed in this German publication foruse in that particular content include methyl diphenyl phosphine, ethyldiphenyl phosphine, propyl diphenyl phosphine, butyl diphenyl phosphine,ethyl-bis(p-methoxy phenyl) phosphine, ethyl-phenyl-p-biphenylphosphine, methyl-phenyl-p(N,N-dimethylaminophenyl) phosphine,propyl-phenyl-p-(N,N dimethylaminophenyl) phosphine, andpropyl-bis-(p-methoxy phenyl) phosphine.

Still other patents and publications also mention the use of certainother alkyl phosphines as ligands in rhodium catalyzed hydroformylationreactions. For example, ethyl ditolyl phosphine is mentioned as apossible ligand by Peterson in U.S. Pat. No. 4,137,240. Wilkinson, U.S.Pat. No. 4,108,905, discloses ethyl diphenyl phosphine as a ligand for arhodium hydrido carbonyl complex, which he says may be used in thepresence of molten triphenyl phosphine as reaction medium. British Pat.No. 2,014,138 discloses the use of, among others, alkyl diarylphosphines, e.g., propyl diphenyl phosphine, in combination with certaindiphosphino alkanes in rhodium hydrido carbonyl complex systems. Boothin U.S. Pat. No. 3,560,539 mentions as a ligand ethyl diphenylphosphine, while Booth et al., U.S. Pat. No. 3,644,446, discloses aspossible ligands ethyl diphenyl phosphine and methyl dixylyl phosphine.Slaugh et al., in U.S. Pat. No. 3,239,566 mentions diphenyl butylphosphine, methyl diphenyl phosphine, ethyl diphenyl phosphine anddiphenyl benzyl phosphine as possible ligands for rhodium or rutheniumcatalysts. Chemistry Letters, (1972) pp. 483-488, refers to a rhodiumcomplex bonded to (+)-diphenylneomenthyl phosphine.

Other Union Carbide researchers disclosed additional inventions mostlyrelated to the commercial TPP-rhodium complex catalyzed process. GermanOffenlegungsschrift 2,715,685 by E. A. V. Brewster and R. L. Pruettdescribed the continuous process in detail. Also, it showed the harmfuleffect of aldehydes having conjugated olefinic unsaturation. GermanOffenlegungsschrift 2,730,527 by R. W. Halstead and J. C. Chatydisclosed the addition of appropriate, minor amounts of oxygen to thereaction mixture of the continuous process to maintain activity.

Alkyl diaryl phosphine ligands were specifically disclosed as potentialrhodium catalyst stabilizer ligands in a number of patents and journalarticles on rhodium catalyzed hydroformylation, U.S. Pat. No. 4,108,905by G. Wilkinson (assigned to Johnson Matthey & Co., Ltd.) disclosedethyl diphenyl phosphine as a stabilizing ligand as a part of an allinclusive, but sparsely supported, disclosure on phosphine ligands.British Patent Application No. 2,014,138 (assigned to Kuraray Co., Ltd.)similarly disclosed bis-diarylphosphino alkanes, i.e., diaryl phosphinesubstituted alkyl diaryl phosphines, as stabilizing ligands. U.S. Pat.No. 4,151,209 by J. L. Paul, W. L. Pieper and L. W. Wade (assigned toCelanese Celanese Corp.) reported on the formation of propyl diphenylphosphine ligand from the TPP-rhodium catalyst during propylenehydroformylation. U.S. Patent Nos. 3,560,539; 3,644,446 and 3,801,646 byF. B. Booth (assigned to Union Oil Co. of California) disclosed thederivation of undefined rhodium catalyst complexes by reduction,starting with a variety of phosphines including methyl diphenylphosphine or propyl diphenyl phosphine. U.S. Pat. No. 3,239,566 by L. H.Slaugh and R. D. Mullineaux (assigned to Shell Oil Co.) disclosed methyldiphenyl phosphine, ethyl diphenyl phosphine and benzyl diphenylphosphine as examples for an all inclusive definition of phosphinecomplexes of rhodium and ruthenium. Slaugh preferred the complexes oftributyl phosphine, started with rhodium chloride and emphasized theformation of alcohols as well as aldehydes in his process.

There are a number of patents which disclosed asymmetrical, opticallyactive alkyl diaryl phosphines for the stereoselective hydroformylationof special olefins such as styrene, e.g., Canadian Pat. No. 1,027,141 byH. B. Tinker and A. J. Solodar (assigned to Monsanto Co.); British Pat.No. 1,402,832 by C. Botteghi, G. Consiglio and C. Salomon (assigned toP. Pino); U.S. Pat. No. 4,139,565 by J. D. Unruh and L. E. Wade(assigned to Celanese Corp.) and French Pat. No. 72.43479 by R. Stern,D. Commereuc, Y. Chavin and H. B. Kagan (assigned to the InstituteFrancais du Petrole, des Carburants et Lubrifiants). Although theseligands are structurally related to those of the present work, theirproperties and application is outside the scope of the presentinvention.

The most conclusive study regarding the effect on hydroformylationcatalysis of an excess of a simple alkyl diphenyl phosphine, i.e., ethyldiphenyl phosphine, was published by A. R. Sanger in the Journal ofMolecular Catalysis [3, pages 221-226, particularly page 222(1977/1978)]. He reported that the addition of ethyl diphenyl phosphineto the TPP-rhodium catalyst resulted in less increase in catalystactivity at 20° C. than that of excess TPP. He found similar effectswhen chelating di-alpha, ω-diphenylphosphino-alkanes were added. Usingmore than molar amounts of 1,4-diphenylphosphino-butane resulted indecreased catalyst activity.

There is much less information on hydroformylation catalysis by therhodium complexes of substituted aliphatic phosphines, particularlysubstituted alkyl diaryl phosphines. Catalyst complexes of suchphosphines are usually within the all inclusive scope of several patentapplications already discussed. However, very few specific disclosureswere made. In effect, no direct disclosure of any tris-(substitutedalkyl diphenyl phosphine) rhodium carbonyl hydride was found prior tothis invention.

In the area of trihydrocarbylsilyl substituted diphenyl phosphinerhodium complexes containing halogen, there are several disclosures byG. Chandra (British Pat. Nos. 1,419,769; 1,420,928 and 1,421,136,assigned to Dow Corning Ltd.). Tris-(trimethylsilyl-methyl diphenylphosphine) rhodium carbonyl chloride is specifically disclosed.Relatively non-selective hydroformylation catalysis by this and similarcomplexes was recently reported by M. O Farrell, C. H. Van Dyke, L. J.Boucher and S. J. Metlin [J. Organomet. Chem., 169 (2) 199 (1979)].

Carboxy substituted t-phosphine rhodium and cobalt complexes of rhodiumwere disclosed in an all inclusive unspecified manner ashydroformylation catalysts in British Pat. No. 1,350,822 by BASF A.G.2-Carboxyethyl diphenyl phosphine was disclosed as an exemplaryphosphine ligand.

Halogen, aryloxy, alkoxy, hydroxy, nitro and phenyl substitutedphosphine rhodium complexes were included in an all inclusive definitionof phosphine rhodium complex hydroformylation catalysts in British Pat.No. 1,298,331 by G. Wilkinson (assigned to Johnson, Matthey & Co., Ltd).However, not a singly substituted alkyl diaryl phosphine compound wasnamed. Similarly, amino, halo and alkyl substituted rhodium complexhydroformylation catalysts were generically disclosed by F. B. Booth inU.S. Pat. No., 3,965,192 (assigned to Union Oil Co. of California) whichwas already referred to. Again, no example of substituted alkyl diarylphosphine was given.

As far as alkyl diphenyl phosphines are concerned, many compounds areknown. However, few aryl or nonhydrocarbyl substituted compounds weredisclosed. A complete list of characterized compounds and theirpreparation, up to 1969, is given in Volume 1, Chapter 1, pages 154 to162 by L. Maier, as a part of the series of monographs, entitled"Organic Phosphorus Compounds" by G. M. Kosolapoff and L. Maier, J.Wiley & Sons, Inc., New York, N.Y., 1972. However, none of theheteroorganic substituted compounds of the present invention isdisclosed. Chapter 3 by G. Booth of the same book also listscharacterized phosphine metal complexes. However, no rhodium carbonylhydrides are found.

With regard to the synthesis of alkyl diphenyl phosphines in general,Kosolapoff and Maier lists a number of displacement reactions as beingfrequently used (see page 2). However, there is little information ondiphenyl phosphine to olefin addition. No substituted alkyl diphenylphosphine derived via addition is disclosed. As far as the hydridocarbonyl rhodium complexes of phosphines are concerned, the known,obviously applicable syntheses, are reviewed in Booth's chapter. They donot include the presently recommended methods.

In the area of the silylalkylphosphine intermediates of the presentinvention, there are several disclosures related to the presentinvention. British Pat. No. 925,721 by H. Niebergall (assigned toKoppers Co., Inc.) broadly disclosed the addition of secondaryphosphines to unsaturated silanes to provide silylalkyl phosphines.British Pat. No. 1,179,242 by W. J. Owen and B. E. Cooper, assigned toMidland Silicones, Ltd., disclosed the preparation of similar compoundsvia displacement reactions of chlorophosphines and silylalkyl Grignardcompounds or sodium phosphines and silylalkyl halides. The preparationof related compounds, i.e., alkoxysilylalkylphosphines was described viaan alternative addition method reacting alkoxysilances and unsaturatedphosphines, by F. Fekete in U.S. Pat. No. 3,067,227, assigned to UnionCarbide Corp. Silylalkylphosphine intermediates useful in thepreparation of the complexes of the present invention were disclosed byJ. K. Jacques and W. J. Owen in British Pat. No. 1,182,763 assigned toAlbright and Wilson (MFG) Ltd., by B. E. Cooper and W. J. Owen in ajournal article on oxidation potentials [see J. Organometal. Chem., 29,33-40 (1971)].

In the area of insoluble, anchored phosphine-transition metal complexcatalysts reactive silyl substituted alkyl diphenyl phosphines wereutilized as intermediates for anchoring. For reference, see U.S. Pat.No. 3,726,809 by K. G. Allum, S. McKenzie and R. C. Pitkethly and U.S.Pat. No. 3,907,852 by A. A. Oswald and L. L. Murrell. Such phosphineanchoring agents had at least one reactive substituent on the silicon.As such, they reacted with the surface hydroxyl group of silica viasiloxane formation.

In contrast to the prior art, it was found in the present invention thattris-(alkyl diaryl phosphine) rhodium carbonyl hydride complexes areattractive selective hydroformylation catalysts in the absence ofTPP-rhodium, dependent on several unexpected conditions. Compared to thewidely studied triphenyl phosphine rhodium complexes, the optimumcatalysis temperature of the present complexes is higher. Higherhydroformylation temperatures using the present catalysts are possiblebecause catalyst stability and selectivity are better maintained.

One of the key unexpected factors in process of the present invention isthat the present catalysts can be employed in a large excess without adrastic loss of catalyst activity. The other factor, also important forhigh selectivity, is the high ratio H₂ to CO. Unexpectedly, the excessof hydrogen does not result in the reduction of the aldehydehydroformylation products to the corresponding alcohols. Coupled withthe high H₂ /CO ratios, it is essential in the present process to employrelatively low pressures, effectively limiting the CO partial pressure.Finally, the continuous process of the present invention isdistinguished by relatively low olefin conversions. These are importantfor both catalysts stability and selectivity.

Due to the above characteristics, the present alkyl diaryl phosphinecomplex catalysts are uniquely suited for an operation wherein thealdehyde product is separated from the catalyst by distillation. Such aspecifically advantageous operation is carried out in a continuousfashion wherein the olefin and synthesis gas feed are continuouslyintroduced into the reactor comprising the catalyst solution and amixture of the aldehyde product and the feed is continuously withdrawnin the gas phase.

The preferred selective process of the present invention, particularlythe combination of the above features, is unique. It is not onlyunexpected in view of the prior art but was described as a process whichshould be inoperative due to the type of phosphine ligands employed.

When compared to the tris-(triphenyl phosphine) rhodium carbonyl hydride(TPP-rhodium) plus triphenyl phosphine based commercial, continuousprocess, the present process exhibits surprising advantages. The alkyldiaryl phosphines of the present process do not undergo P-C bondscission. The only catalyst by-products are the corresponding phosphineoxides. The latter are not inhibitors. The secondary by-products derivedfrom the aldehyde products such as aldehyde trimers do not seriouslyinhibit the present catalytic system either. The present catalysts standout with regard to long term activity maintenance in a continuousprocess. In contrast to the known process, no introduction of oxygenand/or chelating compounds or use of hydroxylic solvent is required foractivity maintenance. As a consequence of higher catalyst stability, thepresent process can be operated at higher temperatures. This, in turn,can lead to an improved product to feed ratio in the distillate of thecontinuous product flash-off process. Also, it extends applicability tohigher olefins and olefin derivatives. In addition, it providesunexpected advantages when employed for combinedhydroformylation-aldolization-hydrogenation processes.

The applicability of the present phosphine ligands unexpectedly butunderstandably depends on their steric requirements, too. Substituentson the alkyl moiety close to the phosphorus were found to inhibitphosphine complexation with rhodium compounds for the first time. Incontrast, substituents outside the immediate proximity of phosphorusresulted in improved complex catalysts. Such substituted phosphinescould be surprisingly advantageously produced via the addition of diarylphosphines to vinyl compounds having activated double bonds.

The alkyl diaryl phosphines of the present invention were found tocomplex with rhodium more strongly than triaryl phosphines. This findingled to a novel method of producing the present catalysts via liganddisplacement, e.g., by the reaction of alkyl diaryl phosphines withtris-(triphenyl phosphine) rhodium carbonyl hydride. According toanother novel method, the present complexes are produced fromacetylacetonato dicarbonyl rhodium either prior to use or in situ underthe reaction conditions.

DISCLOSURE OF INVENTION

The present invention describes novel bis- and tris-(alkyl diarylphosphine) rhodium carbonyl complexes and a novel hydroformylationprocess using said complexes.

The present complexes contain 2 or 3, preferably 3, coordinated alkyldiaryl phosphine moieties per rhodium, 1 to 3, preferably 1, carbonmonoxide ligands per rhodium, and 1 or 0, preferably 1, hydride ligandper rhodium.

The preferred novel complexes are non-charged non-chelated bis- andtris-(alkyl diaryl phosphine) rhodium carbonyl hydrides of the formula

    [Ar.sub.2 P).sub.y R.sub.y.sup.1 ].sub.g [Rh(CO)H].sub.s

wherein Ar is aryl, preferably an independently selected C₆ to C₁₀aromatic unsubstituted or substituted hydrocarbyl radical, morepreferably phenyl, mono-, di- and tri-substituted phenyl, mostpreferably phenyl; R¹ is a C₁ to C₃₀, preferably C₂ to C₂₀, mono-, di-,tri- or tetravalent nonsubstituted or substituted saturated alkyl,including alkyl groups interrupted by noncharged heteroorganic groupssuch as those containing O, N, P, S, Si, with the proviso that if R¹ isa nonsubstituted monovalent alkyl, the minimum number of alkyl carbonsis six; y is the valency of the alkyl group, g times y is 1 to 6,preferably 2 to 6, s is 1 to 3, preferably 2 or 3; said y and s beingselected to satisfy the coordinative valences of rhodium in such amanner that there are 2 or 3, preferably 3, coordinated phosphinemoieties per rhodium, all the aromatic and aliphatic groups and theirsubstituents including nonhydrocarbon groups being chemically stable inhydroformylation systems.

While the value of g, y and h is dependent on the coordinative bondingof the rhodium, the tris-phosphine rhodium complex compositions areunexpectedly stable and as such preferred. In the case of monovalentalkyl, preferably substituted alkyl, diaryl phosphine rhodium complexes,the preferred compositions are accordingly of the formula

    (Ar.sub.2 PR.sup.1).sub.g Rh(CO)H

wherein R¹ is a monovalent alkyl as previously defined, preferably asubstituted alkyl; g is 1 to 3, preferably 2 or 3, more preferably 3,and, of the formula

    (Ar.sub.2 PR.sup.1).sub.3 Rh(CO)H

The alkyl diaryl phosphine complex catalyst compositions of the presentinvention include compounds containing positively charged rhodium. Thesecomplexes are preferably of the general formula

    [(Ar.sub.2 PR.sup.1).sub.2 Rh.sup.+ (CO).sub.3 ]X.sup.-

wherein the meaning of Ar and R¹ is the same as before and X⁻ is ananion, preferably a non-coordinating anion, preferably selected from thegroup consisting of borate, aluminate, perchlorate, sulfonate, nitrate,fluorophosphate, fluorosilicate such as Ph₂ B⁻, F₄ B⁻, ClO₄ ⁻, Ph₃ SO₃⁻, NO₃ ⁻, F₆ P⁻, F₆ Si²⁻.

The preferred substituents of the aromatic groups are C₁ to C₃₀,preferably C₁ to C₁₂ alkyl, alkoxy, acyl, acyloxy, acrylamido,carbamido, carbohydrocarbyloxy, halogen, phenoxy, hydroxy, carboxy.These substituents are preferably bound to a phenyl group. Mono- anddisubstituted phenyl groups are preferred.

Examples of the aromatic groups are phenyl, fluorophenyl,difluorophenyl, tolyl, xylyl, benzoyloxyphenyl, carboethoxyphenyl,acetylphenyl, ethoxyphenyl, phenoxyphenyl, biphenyl, naphthyl,hydroxyphenyl, carboxyphenyl, trifluoromethylphenyl, tetrahydronaphthyl,furyl, pyrryl, methoxyethylphenyl, acetamidophenyl,dimethylcarbamylphenyl.

The alkyl groups are primary and secondary alkyl groups, preferablyprimary alkyl groups. Next to the preferred primary α-carbons of thealkyl groups, the β-carbons are primary and secondary, preferably alsoprimary. Accordingly, a preferred class of complexes is of the generalformula

    [Ar.sub.2 PCH.sub.2 CH.sub.2 R'].sub.3 Rh(CO)H

wherein R' is a C₄ to C₂₈, nonsubstituted or substituted alkyl of apreferably branched or cyclic character; a non-substituted orsubstituted C₆ to C₁₀ aryl, preferably phenyl; a nonhydrocarbyl group,preferably selected from organic radicals containing silicon, oxygen,nitrogen and phosphorus. The heteroatoms of the organic radicals arepreferably of the trihydrocarbyl silane, hydroxy, ether, acyl, amine,amide, and phosphine oxide. The heteroatom is preferably directly boundto the β-methylene group.

The preferred substituents of the primary alkyl groups are the same.Some more preferred substituted alkyl diaryl phosphine complexes will bedefined later.

Exemplary alkyl groups are methyl, n-hexyl, docosyl, triacontyl,fluoropropyl, perfluoroethyl-ethyl, isopropyl, primary isobutyl,cyclopentyl, t-butylethyl, cyclohexylethyl, phenylethyl,trimethylsilylethyl, hydroxy, methoxyethoxyethyl, acetylethyl,pyrrolidinonylethyl, tributylphosphonium substituted ethyl, tris-hydroxysubstituted t-butylethyl, triphenylmethylethyl, hydroxypropyl,carbomethoxyethyl, phenoxyethyl, benzamidoethyl, benzoyloxyethyl,pyrrylethyl, furylethyl, thienylethyl. The nonhydrocarbyl, i.e.,heteroorganic R' groups will be further defined.

The alkyl groups as defined by R' are mono- or polyvalent alkyl groups,their valence ranging from 1 to 4. The polyvalent groups may have acarbon skeleton or can be interrupted by appropriate heteroatoms such asoxygen, sulfur, nitrogen, silicon.

Exemplary polyvalent alkyl groups are tetramethylene, xylylene,oxy-bis-propyl, sulfone-bis-propyl, nitrilo-tripropyl,silicone-tetraethyl, cyclohexylene diethyl, keto-bis-ethyl.

A class of the alkyl groups is represented by aliphatic hydrocarbylgroups. Preferred subgroups of the latter are n-alkyl groups andhydrocarbyl substituted n-alkyl groups. When R¹ is one of these twosubgroups, the preferred complexes are of the formula

    [Ar.sub.2 P(CH.sub.2).sub.n CH.sub.3 ].sub.h Rh(CO)H

and

    [Ar.sub.2 P(CH.sub.2).sub.m R"].sub.h Rh(CO)H

wherein n is C₆ to C₃₀ and m is 1-22, preferably 2 to 22, morepreferably 2 or 3 h is 2 or 3, R" is a C₃ to C₂₇ branched alkyl,cycloalkyl, aryl, such as isopropyl, t-butyl, cyclohexyl, phenyl.

The choice of aryl and alkyl groups and their substituents is limitedonly by stereochemical and reactivity considerations. Stericallydemanding groups inhibit the formation of the present tris-phosphinecomplexes. Groups which are reactive under the use conditions of thepresent complexes are apparently undesirable as catalysts.

A preferred broad class of bis- or tris-alkyl diaryl phosphine complexesis of the general formula

    [(Ar.sub.2 PQ).sub.b E.sup.y R.sub.y-b ].sub.g. (RhX.sub.n).sub.s I

wherein Ar is an aryl group containing from 6 to 10 carbon atoms;

Q is a saturated divalent organic radical selected from an alkyleneradical and an alkylene radical the carbon chain of which is interruptedwith either oxygen or phenylene groups, wherein the alkylene radicalcontains from 2 to 30 carbon atoms;

E is a member selected from ##STR1## --O-- and --S--, wherein R⁹ is amember selected from H, an alkyl group containing 1 to 30 carbon atomsand an aryl group containing from 6 to 10 carbon atoms, and wherein x isan integer of 0 or 1 with the proviso that at least one x is 1;

y represents the number of bonds available from the group E forattachment to the groups Q and R;

R represents a member selected from an alkyl group containing from 1 to28 carbon atoms and an aryl group containing from 6 to 10 carbon atomsand when E is --N, R also represents a member selected from ##STR2##which together with the N atom forms a heterocyclic ring, wherein R⁴,R⁵, R⁶, R⁷ and R⁸ are hydrocarbyl radicals such that said heterocyclicring contains from 5 to 6 atoms;

b is an integer of from 1 to 4, provided that y-b is not less than zero,

X is an anion or organic ligand, excluding halogen, satisfying thecoordination sites of the rhodium metal; RhX_(n) is preferably Rh(CO)H

g times b is 1 to 6;

n is 2 to 6; and

s is 1 to 3.

A preferred class of compounds of the invention are compounds of theformula

    [(Ar.sub.2 PQE.sup.y R.sub.y-1).sub.2 Rh.sup.+ (CO).sub.3 ]G.sup.-

wherein Ar, Q, E, y and R are as defined above and G⁻ is an anion,preferably a non-coordinating anion. Suitable G⁻ anions include borates,aluminates, perchlorates, sulfonates, nitrates, fluorophosphates andfluorosilicates, such as Ph₄ B⁻, F₄ B⁻, ClO₄ ⁻, Ph₃ SO₃ ⁻, CF₃ SO₃ ⁻,NO₃ ⁻, F₆ P⁻ and F₆ Si⁻².

A preferred class of alkyl diphenyl phosphine rhodium complexes is ofthe following formula

    (Ar.sub.2 PQY).sub.h Rh(CO)H

and

    [Ar.sub.2 P(CH.sub.2).sub.m Y].sub.h Rh(CO)H

wherein Ar and h have the previously defined meaning, m is 1 to 30,preferably 2 to 22, more preferably 2 or 3, most preferably 2; Q is a C₁to C₃₀, preferably C₂ to C₂₂, more preferably a C₂ to C₃, mostpreferably a C₂ unsubstituted or substituted, preferably unsubstituted,saturated straight chain divalent organic radical, more preferably apolymethylene radical which can be interrupted by either oxygen andphenylene; Y is a noncharged organic, preferably hetero-organicsubstituent, preferably with 3 to 30 carbon atoms, having a highersteric requirement than methylene and polymethylene such astrihydrocarbylsilyl, quaternary tetraalkyl phosphonium, heterocyclictertiary nitrogen, phosphine oxide, sulfone, carbonyl, carboxylate orsterically demanding hydrocarbon groups, the latter being exemplified byphenyl, triphenylmethyl, t-butyl, trishydroxy substituted butyl and thelike.

As far as novel compounds having phosphorus based heteroorganicsubstituents for Y are concerned, chelate forming amines, phosphines andphosphonium salts are excluded from this application. Y is preferably aC₁ to C₃₀, preferably C₁ to C₁₀, organic radical selected from the groupconsisting of substituted and unsubstituted secondary and tertiaryalkyl, substituted and unsubstituted aryl, preferably phenyl andheteroorganic radicals. The heteroorganic radicals are defined asradicals having an atom, with an unsatisfied valency to be bound to Q,which is either a carbon having a hetero-atom substituent or is aheteroatom itself. The heteroatoms are preferably oxygen, sulfur,phosphorus, silicon and nitrogen, more preferably carbonyl, O, sulfone,S, phosphine or phosphine oxide, P, silane, Si, and amide, N.Heteroorganic radicals, especially silyl radicals, are most preferred.

If the Q is substituted, the substituents are the same as previouslydefined for Ar and R. Exemplary Q radicals are ethylene, butylene,docosamethylene, tricontamethylene, phenyl bis(ethyl), ethylenebis(oxyethyl), ethylene-bis oligo (oxyethyl), oxy ethyl propyl, oxyethyl perfluoroethyl, oxy ethyl hydroxypropyl.

When Y is an alkyl radical, it is preferably saturated open chain and/orcyclic. The preferred substituent is hydroxy. Unsubstituted secondaryand tertiary alkyl radicals are another preferred type.

In case Y is an aryl radical, it is preferably substituted orunsubstituted phenyl, most preferably phenyl.

Oxygen based heteroorganic radicals for Y are hydroxy, carbonyl,carboxylate, acyloxy, ether, more preferably hydroxy, ether carbonyl,acyloxy. Sulfur based heteroorganic radicals are thiyl and sulfonyl.Phosphorus based heteroorganic radicals are diarylphosphino,dihydrocarbylphosphate, dihydrocarbylphosphonate,dihydrocarbylphosphite. Nitrogen based heteroorganic radicals are aminoand those of reduced basicity, i.e., amido, ureido, imido, amine oxide,bis-(hydroxyethyl) amine. Cyclic amido, such as N-2pyrrolidinonyl, ispreferred.

Exemplary Y radicals are the following: trimethylsilyl, tripropylsilyl,triphenylsilyl, --diphenyl phosphine oxide, diisobutyl phosphine oxide,diphenyl phosphine, dihydroxypropyl phosphine, dipropyl phosphite,diphenyl phosphate, tributyl phosphonium benzene sulfonate,didecyldibutyl phosphonium tetraphenyl borate, benzyl dicyclohexylphosphonium methane sulfonate--pyrryl, dimethylpyrryl, pyrrolidinonyl,morpholinyl, acetamido, benzamido, amido, carbamido, ureido,bis-hydroxyethylamino, --phenyl sulfone, fluorophenyl sulfone, ethylsulfone, ethylthio, phenylthio--acetyl, benzoyl, carbomethoxy,benzoyloxy, carbobenzoxy, acetate, benzoate, phenylacetate, hydroxy,carbamate, phenoxy; i-propyl, phenoxyphenyl, diisobutyl, cyclopentyl,diisopropylamino, anilino, diphenylamino, furyl, mesityl,pentafluorophenyl, tetrahydronaphthyl tris(hydroxymethyl) methine.

In case Q is bound to a y+1 valent heteroorganic radical, E, thehydrocarbyl substituents of E are indicated by the symbol R"':

    (Ar.sub.2 PQER.sub.y "').sub.h Rh(CO)H

and

    (Ar.sub.2 P(CH.sub.2).sub.m ER.sub.y "')Rh(CO)H

wherein the meaning of Ar, Qh and m is the same as defined previously; Eis the inorganic part of the heteroorganic radical, ER_(y) "' is anoncharged, nonchelating heteroorganic radical selected from the groupconsisting of silane silicone, ether, ester, keto and hydroxy oxygen,phosphine and phosphorus ester phosphorus, amine, amide, amine oxide andheterocyclic nitrogen, sulfide and sulfone sulfur; and R"' is anindependently selected C₁ to C₃₀, preferably C₁ to C₁₀, substituted orunsubstituted, preferably unsubstituted or monosubstituted, morepreferably unsubstituted hydrocarbyl radical. R"' is preferably selectedfrom the group of hydrocarbyl radicals consisting of C₁ to C₆ alkyl, C₅and C₆ cycloalkyl, phenyl, C₁ to C₆ monosubstituted alkyl,monosubstituted phenyl. More preferably, R"' is C₁ to C₆ alkyl orphenyl. As such, the R"' groups include methyl, propyl,ω-trifluoropropyl, pentafluoropropyl, pentafluorophenylethyl, phenyl,cyclotetramethylene, tolyl, methylcyclopentyl, decyl, fluoropropyl,benzyl, cyclohexyl, fluoropentyl, methoxyethyl, tricosyl, hydroxyethyl,methoxyethoxylethyl. Further examples of R"' were given when listingexamples of the Ar and R' hydrocarbyl groups.

A similar class of complexes possesses a positively charged rhodiummoiety with the general formula

    [(Ar.sub.2 PQY).sub.2 Rh.sup.+ (CO).sub.3 ]X.sup.-

wherein all the symbols possess the previously defined meanings.

Another preferred class of compounds of the present invention includesome of those compounds disclosed in our copending U.S. application Ser.No. 11,238 filed Feb. 12, 1979 now U.S. Pat. No. 4,298,541, of which thepresent application is a Continuation-In-Part. The particulartrihydrocarbyl silyl substituted alkyl diaryl phosphine complexesthereof which are included within the scope of the present invention arethose of the formula

    [(Ar.sub.2 PQ).sub.b SiR.sub.4-b ].sub.g (RhX.sub.n).sub.s

wherein Ar, Q, b, R, g, X, n and s as defined above. Particularlypreferred complexes within this class are complexes of the formulas

    [(Ar.sub.2 P(CH.sub.2).sub.m).sub.b SiR.sub.4-b ].sub.g [Rh(CO)H].sub.s,

    [(Ph.sub.2 PQ).sub.b SiR.sub.4-b ].sub.g [Rh(CO)H].sub.s,

    [Ph.sub.2 P(CH.sub.2).sub.m).sub.b SiR.sub.4-b ].sub.g [Rh(CO)H].sub.s,

    ((Ar.sub.2 P(CH.sub.2).sub.m).sub.2 Si(CH.sub.3).sub.2 ].sub.3 [Rh(CO)H].sub.2

    (Ph.sub.2 PQSiR.sub.3).sub.3 Rh(CO)H,

    (Ph.sub.2 P(CH.sub.2).sub.m SiR.sub.3).sub.3 Rh(CO)H,

    [(Ph.sub.2 P(CH.sub.2).sub.m).sub.4 Si].sub.3 Rh(CO)H].sub.4

    (Ar.sub.2 PQSiR.sub.3).sub.2 Rh.sup.+ (CO).sub.3 G.sup.-,

    [Ar.sub.2 P(CH.sub.2).sub.m SiR.sub.3 ].sub.2 Rh.sup.+ (CO).sub.3 G.sup.-, and

    [Ar.sub.2 P(CH.sub.2).sub.m SiR.sub.3 ].sub.2 Rh.sup.+ (CO).sub.3 (BPh.sub.4.sup.-)

wherein the symbols are as defined above. Particularly preferredcompounds are

    (Ph.sub.2 P(CH.sub.2).sub.2 Si(CH.sub.3).sub.3).sub.3 RH(CO)H

    (Ph.sub.2 P(CH.sub.2).sub.3 Si(CH.sub.3).sub.3).sub.3 Rh(CO)H

    (Ph.sub.2 P(CH.sub.2).sub.2 Si(C.sub.3 H.sub.7).sub.3).sub.3 Rh(CO)H

    (Ph.sub.2 P(CH.sub.2).sub.2 SiPh.sub.3).sub.3 Rh(CO)H

    ((Ph.sub.2 PCH.sub.2 CH.sub.2).sub.2 Si(CH.sub.3).sub.2).sub.3 Rh(CO)H

Still another preferred class of novel compounds within the scope of thepresent invention include those in which E represents a tertiary carbongroup, i.e., catalysts of the formulae

    [(Ar.sub.2 PQ).sub.b CR.sub.4-b ].sub.g.(RhX.sub.n).sub.s

and

    (Ar.sub.2 PQCR.sub.3).sub.3 Rh(CO)H

wherein Ar, Q, R, X, b, g, n and s are as defined above. A particularlypreferred class of such compounds include those of the formula

    (Ph.sub.2 P--CH.sub.2 --.sub.m CR.sub.3).sub.3 Rh(CO)H

wherein m is an integer of from 1 to 30 and R is as defined above.Examples of such catalysts include

    (Ph.sub.2 PCH.sub.2 C(CH.sub.3).sub.3).sub.3 Rh(CO)H,

    [Ph.sub.2 PCH.sub.2 CH.sub.2 C(CH.sub.3).sub.3 ].sub.3 Rh(CO)H

and

    (Ph.sub.2 PCH.sub.2 CH.sub.2 CH.sub.2 C(CH.sub.3).sub.3).sub.3 Rh(CO)H.

A further preferred class of compounds within the scope of the presentinvention include keto substituted compounds of the formulas ##STR3##wherein Ar, Q, R, X, b, g, n and s are as defined above. Of suchcompounds particularly preferred are acyl compounds of the formula##STR4## wherein m is an integer of from 1 to 30, especially from 2 to14, and R is as defined above. Examples of such catalysts include##STR5##

Catalysts having carbohydrocarbyloxy substituted phosphines are of theformulae ##STR6## wherein Ar, Ph, Q, R, b, X, g, m, n and s are asdefined above, represent another preferred class of compounds inaccordance with the present invention. Particularly preferred arecompounds of the formula ##STR7## wherein m is an integer of from 2 to22, especially from 4 to 14, and R is as defined above. Examples ofcompounds within this class include ##STR8##

The corresponding acyloxy complexes are also included within the novelcarboxylate substituted complexes of the present invention. Thesecomplexes are of the formula ##STR9## wherein Ar, Q, R, X, b, g, n, mand s are as defined above. Exemplary of suitable compounds within thisclass is ##STR10## wherein Ph is phenyl.

Non-chelating trivalent nitrogen substituted complexes of the formula

    [(Ar.sub.2 PQ).sub.b NR.sub.3-b ].sub.g [RhX.sub.n ].sub.s

wherein Ar, Q, b, g, s, n, R and X are as defined above, representanother class of preferred compounds of the invention. These complexesinclude non-chelating open chain amino substituted alkyl diarylphosphine complexes and nitrogen-containing heterocyclic ringsubstituted alkyl diaryl phosphine complexes. The latter include cyclicamides and imides. Preferred complexes within this class include aminosubstituted complexes of the formulas: ##STR11## wherein Ar, Q, b, R, g,s, R⁴, R⁵, R⁶, R⁷, R⁸ and Ph are as defined above and p is an integer offrom 1 to 12.

Examples of such compounds include ##STR12##

Another class of nitrogen-containing complexes of the invention areamide substituted open chain alkyl diaryl phosphine complexes of theformula ##STR13## wherein Ar, Q, b, g, s, n, R⁹, R and X are as definedabove. Preferably, R⁹ is H, an alkyl group containing 1 to 6 carbonatoms or phenyl. Preferred complexes within this class are of theformulas: ##STR14## wherein Ar, Q, R₉, R, m and Ph are as defined above.

Examples of such compounds are (Ph₂ PCH₂ CH₂ CONH₂)₃ Rh(CO)H and (Ph₂PCH₂ CH₂ CON(CH₃)₂)₃ Rh(CO)H.

The novel complexes of the invention also include carbamic acidderivatives of alkyl diaryl phosphine complexes of the formulae:##STR15## wherein Ar, Q, R⁹, b, g, n, s and X are as defined above.Preferred complexes within this class include ##STR16## wherein thesymbols have the above defined meanings. An example of such a compoundis (Ph₂ PCH₂ CH₂ CN(CH₃)₂)₃ Rh(CO)H.

The novel compounds of the present invention also include trivalentphosphorus derivatives of the formula ##STR17## wherein Ar, Q, R, X, b,x, g, n and s are as defined above. Examples of such compounds include

    [Ar.sub.2 PQOP(OR).sub.2 ].sub.3 Rh(CO)H

    [Ar.sub.2 P(CH.sub.2).sub.m OP(OR).sub.2 ].sub.3 Rh(CO)H

and

    ((Ar.sub.2 P(CH.sub.2).sub.m O).sub.3 P).sub.3 Rh(CO)H

wherein Ar, Q, R and m are as defined above. A preferred complex is

    ((PH.sub.2 PCH.sub.2 CH.sub.2 CH.sub.2 O).sub.3 P).sub.3 Rh(CO)H.

The diaryl phosphine substituted derivative catalysts are non-chelatingcompounds of the formula

    [Ar.sub.2 PQPAr.sub.2 ].sub.3 Rh(CO)H

    [A.sub.2 P(CH.sub.2).sub.m PAr.sub.2 ].sub.3 Rh(CO)H

In the case of these compounds, m is 4 to 22, more preferably 6 to 14.Such compounds are

    [Ph.sub.2 (CH.sub.2).sub.4 PPh.sub.2 ].sub.3 Rh(CO)H

    [Ph.sub.2 (CH.sub.2).sub.14 PPh.sub.2 ].sub.3 Rh(CO)H

    [Ph.sub.2 (CH.sub.2).sub.6 PPh.sub.2 ].sub.3 Rh(CO)H

Still another preferred class of compounds in accordance with thepresent invention include higher valent phosphorus derivatives of theformula ##STR18## Preferred complexes within this class are ##STR19##wherein Ar, Q, R, X, b, x, g, n, Ph and s are as defined above. Apreferred compound is of the formula ##STR20## wherein m is an integerof from 1 to 30, especially from 2 to 14, and R is defined as above. Oneexample of this type catalyst is ##STR21##

Still another group of novel compounds within the scope of the presentinvention are the sulfone derivatives of the formula

    [(Ar.sub.2 PQ).sub.b SO.sub.2 R.sub.2-b ].sub.g (RhX.sub.n).sub.s

wherein Ar, Q, R, b, g, n, s and X are as defined above. Preferredcomplexes within this class include complexes of the formulae

    [Ar.sub.2 PQSO.sub.2 R].sub.3 Rh(CO)H

    [Ar.sub.2 P(CH.sub.2).sub.m SO.sub.2 R].sub.3 Rh(CO)H

    ([Ar.sub.2 P(CH.sub.2).sub.m ].sub.2 SO.sub.2).sub.3 [Rh(CO)H].sub.2

and

    [Ar.sub.2 PCH.sub.2 CH.sub.2 SO.sub.2 R].sub.3 Rh(CO)H

wherein Ar, Q, R, X, b, g, n, m and s are as defined above. A specificexample of a compound within this class is

    [Ph.sub.2 CH.sub.2 CH.sub.2 SO.sub.2 C.sub.2 H.sub.5 ].sub.3 Rh(CO)H

Ether derivatives of alkyl diaryl phosphine complexes of the formula

    [(Ar.sub.2 PQ).sub.b OR.sub.2-b ].sub.g (RhX.sub.n).sub.s

wherein Ar, Q, R, g, b, n, s, and X are as defined above, form anotherclass of the novel complexes of the invention. Preferred complexeswithin this class include complexes of the formulae:

    [Ar.sub.2 PQOR].sub.3 Rh(CO)H

    [Ar.sub.2 P(CH.sub.2).sub.m OR].sub.3 Rh(CO)H

    [Ar.sub.2 P(CH.sub.2 CH.sub.2 O).sub.3 CH.sub.3 ].sub.3 Rh(CO)H

    [Ar.sub.2 PCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH].sub.3 Rh(CO)H

and

    ((Ar.sub.2 P(CH.sub.2).sub.m O).sub.3 P).sub.3 Rh(CO)H

wherein Ar, Q, R and m are as defined above. Exemplary of suitablecompounds within this class is

    [Ph.sub.2 PCH.sub.2 CH.sub.2 OPh].sub.3 Rh(CO)H.

Also included within the scope of the novel complexes in the inventionare hydroxy derivatives of the formulas

    [Ar.sub.2 PQOH].sub.g (RhX.sub.n).sub.s

    (Ar.sub.2 PQOH).sub.3 Rh(CO)H

    [Ar.sub.2 P(CH.sub.2).sub.m OH].sub.3 Rh(CO)H

and

    [Ar.sub.2 PCH.sub.2 CH(OH)CH.sub.2 OH].sub.3 Rh(CO)H

wherein Ar, Q, X, n, m, g and s are as defined above. Exemplary of asuitable compound within this class is

    [Ph.sub.2 PCH.sub.2 CH.sub.2 CH.sub.2 OH].sub.3 Rh(CO)H

Yet another class of novel compounds within the present invention arethioether derivatives of the formulae

    [(Ar.sub.2 PQ).sub.b SR.sub.2-b ].sub.g Rh(CO)H

    [Ar.sub.2 PQSR].sub.3 Rh(CO)H

and

    (Ar.sub.2 P(CH.sub.2)mSR).sub.3 Rh(CO)H

wherein Ar, Q, R, X, b, g, n, m and s are as defined above. Exemplary ofsuitable compounds within this class is

    [Ph.sub.2 PCH.sub.2 CH.sub.2 CH.sub.2 SPh].sub.3 Rh(CO)H.

The diaryl alkyl phosphine ligands employed in the present invention areprepared by any number of standard techniques. One preferred synthesistechnique involves the addition of diaryl alkyl phosphines to suitableunsaturated compounds:

    bAr.sub.2 PH+[CH.sub.2 ═CH--D--.sub.b E.sup.y R.sub.y-b →[Ar.sub.2 PCH.sub.2 CH.sub.2 --D--.sub.b E.sup.y R.sub.y-b

or

    [Ar.sub.2 PQ].sub.b E.sup.y R.sub.y-b

wherein CH₂ ═CHD-- after the reaction represents the group Q as definedabove. Thus, D can be a covalent bond or the remainder of the group Qother than --CH₂ --CH₂ --. Preferably --D-- represents --CH₂ --_(k)wherein k ranges from 0 to 28, especially from 0 to 6 and mostpreferably from 0 to 1. Such additions are preferably carried out via aradical chain mechanism in a free radical manner. Chemical and/orradiation initiators can be used. It has been found that the selectivityof such reactions can be improved by using an excess of phosphinereactant, preferably from 5 to 100% excess over the stoichiometricamount required of the phosphine. A suitable chemical initiator for thisprocess is a labile azo compound such as azo-bis-i-butyronitrile. Theamount of the initiator can vary depending upon the chain length of thereaction and preferably is in the range of from about 0.1 to about 3%.The reaction temperature of a chemically initiated addition depends uponthe temperature of initiating radical generation. This initiationnormally occurs in the range of from 0° to 50° C.

For radiation initiation of the above-described addition reaction,ultraviolet light or gamma irradiation can be employed. The radiationintensity and duration are highly dependent upon the chain length, i.e.,the G value. The preferred temperature of radiation initiation isbetween about -90° C. and +90° C.

The above-described radical addition of diaryl phosphines to certainsubstituted vinylic compounds is unexpectedly selective and fast. Suchsubstituted vinylic compounds include vinyl silanes, vinyl ketones,N-vinyl amides, acrylates, and sulfones, as illustrated by the followingformulas:

    Ar.sub.2 PH+(CH.sub.2 ═CH).sub.b SiR.sub.4-b →(Ar.sub.2 PCH.sub.2 CH.sub.2).sub.b SiR.sub.4-b

    Ar.sub.2 PH+CH.sub.2 ═CHSiR.sub.3 →Ar.sub.2 PCH.sub.2 CH.sub.2 SiR.sub.3

    Ar.sub.2 PH+CH.sub.2 ═CHNR.sup.9 COR→Ar.sub.2 PCH.sub.2 CH.sub.2 NR.sup.9 COR ##STR22##

    Ar.sub.2 PH+CH.sub.2 ═CHCOR→Ar.sub.2 PCH.sub.2 CH.sub.2 COR

    Ar.sub.2 PH+CH.sub.2 ═CHCO.sub.2 R→Ar.sub.2 PCH.sub.2 CH.sub.2 CO.sub.2 R

    Ar.sub.2 PH+CH.sub.2 ═CHSO.sub.2 R→Ar.sub.2 PCH.sub.2 CH.sub.2 SO.sub.2 R

The high reactivity of these substituted vinylic compounds is contrastedwith the sluggish behavior of some other substituted olefins havinganalogous structures, e.g., t-butyl ethylene.

It has also been observed that additions of phosphines to vinyliccompounds wherein k=O occur with ease in the presence of radiationparticularly ultraviolet light. The reactivity of such vinyl compoundsis in marked contrast to the rather sluggish behavior of olefins havinganalogous structures. In addition to such vinyl compounds, allylcompounds wherein k=1 are another preferred class of reactant.

Similar anti-Markovnikov additions can be carried out via anionicmechanism with base catalysis to certain conjugated vinylic compoundssuch as acrylates. Such anionic addition can be performed with eitheradded base catalysis, e.g., a quaternary base addition, or without anybase added in addition to the phosphine base.

Another technique which may be employed in the preparation of the alkyldiaryl phosphine ligands involved in the present invention is theaddition of suitable hydrogen-containing compounds to unsaturatedphosphines, preferably vinyl diaryl phosphines:

    bAr.sub.2 P--D--CH═CH.sub.2 +H.sub.b E.sup.y R.sub.y-b →[Ar.sub.2 P--D--CH.sub.2 --CH.sub.2 --.sub.b E.sup.y R.sub.y-b

or

    [Ar.sub.2 PQ].sub.b E.sup.y R.sub.y-b

wherein D is defined as above. Again, D preferably represents --CH₂--_(k) wherein k is an integer of from 0 to 28. The preferred reactantsare the vinylic and allylic materials, this time the phosphines. Thus,the heteroorganic substituted alkyl diaryl phosphines are derived byemploying compounds such as secondary phosphine oxide, dihydrocarbylhydrogen phosphites and thiols as the hydrogen-containing compound.

The above approach is exemplified by the free radical addition ofsecondary phosphine oxides, hydrogen phosphites and thiols: ##STR23##wherein Ar, k and R are as defined above. It is surprising that similaradditions could not be carried out using silanes as adding agents. Ingeneral, the reaction conditions for the successful radical additionswere those previously described for the diaryl phosphine olefinadditions.

The method for preparing non-chelating bis-phosphines is described inthe application of Alexis A. Oswald filed Jan. 23, 1980 entitled"Tetraalkyl Phosphonium Substituted Phosphine and Amine Metal Complexesand Processes for Use Thereof" now U.S. Pat. No. 4,302,401. Thatapplication also discloses methods for the synthesis of trialkylphosphonium substituted alkyl diaryl phosphines and is incorporatedherein by reference.

Other methods for alkyl diaryl phosphine ligand preparation employdisplacement reactions. One type of reaction starts with diarylphosphides, particularly alkali, metal phosphides, and suitable chloro-,bromo-, or iodo-alkyl compounds:

    bAr.sub.2 PMe+[LQ].sub.b E.sup.y R.sub.y-b →[Ar.sub.2 PQ].sub.b E.sup.y R.sub.y-b +bMeL

wherein Me is Na, K, Li and L is Cl, Br, I. Another technique startswith diaryl chloro or bromo phosphines and the corresponding Grignardderivatives of suitable alkyl compounds:

    bAr.sub.2 PJ+[JMgQ].sub.b E.sup.y R.sub.y-b →[Ar.sub.2 PQ].sub.b E.sup.y R.sub.y-b +bMgJ.sub.2

wherein J is chlorine or bromine and the other symbols are as definedabove.

For the preparation of the present complexes, standard methods ororganometallic chemistry are discussed in a comprehensive text,"Advanced Inorganic Chemistry," by F. A. Cotton and G. Wilkinson(Interscience Publishers, New York, 1972) and exemplified in the serieson "Inorganic Syntheses" particularly Volume XV, edited by G. W.Parshall and published by McGraw-Hill Book Co., New York, 1974, and inU.S. Pat. No. 4,052,461 by H. B. Tinker and D. E. Morris, assigned toMonsanto Co.

For the preparation of the rhodium complexes, one of the specificallypreferred direct methods of synthesis starts with rhodium chloride. Thismethod can be employed, e.g., for the synthesis of tris-(alkyl diarylphosphine) rhodium carbonyl hydride complexes according to the followinggeneral scheme: ##STR24##

Other preferred direct methods of complex preparation include thereaction of transition metal carbonyls or oxides, such as those ofrhodium with suitable diaryl alkyl phosphine ligand and CO/H₂.Similarly, organic salts of transition metals such as acetates can bereacted with the diaryl alkyl phosphine ligand.

According to one preferred method, the rhodium reactant is a rhodiumsalt, preferably rhodium trichloride or its hydrate. This methodpreferably employs a base, most preferably KOH or sodium borohydride,and a reducing carbonylating agent such as formaldehyde, hydrogen and COto produce the carbonyl hydride complex via the tris-(alkyl diarylphosphine) rhodium chloride and its carbonyl derivative intermediatecompounds.

The complexes of the invention can also be prepared via an indirectmethod by reaction of the corresponding complexes of a triarylphosphine, preferably triphenyl phosphine, with the desired diarylalkylphosphine ligand, preferably in excess, e.g.:

    (Ph.sub.3 P).sub.3 Rh(CO)H+3Ar.sub.2 PQE.sup.y R.sub.y-1 →(Ar.sub.2 PQE.sup.y R.sub.y-1).sub.3 Rh(CO)H+3Ph.sub.3 P

In general, the alkyl diaryl phosphine ligands are more basic than thecorresponding triaryl phosphines. This basicity difference is a positivefactor in the above ligand substitutions, providing completely orpartially exchanged complexes, e.g.: ##STR25##

The formation of the tris(alkyl diaryl phosphine) rhodium carbonylhydride complexes via ligand exchange can be followed by ³¹ P nuclearmagnetic resonance. ³¹ P nmr can be also used for the identification andthe quantitative determination of the starting alkyl diaryl phosphinereactants. As the ion exchange proceeds in an appropriate inert solvent,preferably aromatic hydrocarbon, ³¹ P nmr shows the number and amountsof the different phosphine species. When an excess of the theoreticallyrequired alkyl diaryl phosphine reactant, preferably more than 100%excess, is used, the formation of the tris(alkyl diaryl phosphine)complex is essentially quantitative. The reaction temperature is between10° and 100° C., usually ambient temperature.

Ligand exchange methods can be used for the preparation of the presentcomplexes in situ, e.g., under hydroformylation conditions. For thispurpose, the various rhodium carbonyls, and appropriate organic salts ofrhodium carbonyl are particularly preferred. For example, dicarbonylacetylacetonato (AcAc⁻) dicarbonyl rhodium can be reacted with hydrogenand an excess amount of alkyl diaryl phosphine:

    Rh.sup.+ (CO).sub.2 (AcAc.sup.-)+3Ar.sub.2 PR+H.sub.2 →(Ar.sub.2 PR).sub.3 Rh(CO)H+CO+(CH.sub.3 CO).sub.2 CH.sub.2

The synthesis and the physicochemical constants of most of the knownphosphines is given in Volume 1 of a series of monograph, entitled"Organic Phosphorus Compounds," edited by G. M. Kosolapoff and L. Maier,published by J. Wiley and Sons, Inc., New York, N.Y., in 1972.Particularly, Chapter 1 on "Primary, Secondary and Tertiary Phosphines,"by L. Maier, is relevant. Specifically, pages 33 to 105 and 135 to 224provide the information on the certain tertiary phosphines used in thepresent invention. Chapter 3A, particularly pages 433 to 493, on"Phosphine Complexes with Metals" by G. Booth of the same volume alsoprovides general information regarding phosphine rhodium complexes.

The novel complexes of the present invention have been found to beparticularly useful in carbonylation reactions, particularlyhydroformylation reactions, which involve the reaction of unsaturatedorganic compounds with CO, or CO and hydrogen mixtures. Carbonylationreactions are generally reactions of unsaturated organic compounds withcarbon monoxide plus preferably a third reactant. Carbonylations aredescribed in detail in the earlier referenced Falbe monograph. Maintypes of carbonylations catalyzed by the present complexes are theRoelen reaction (hydroformylation) of olefins with CO and H₂ andsubsequent aldolization reactions: the Reppe reaction (metal carbonylcatalyzed carbonylation) mainly of olefins, acetylenes, alcohols andactivated chlorides with CO alone or with CO plus either alcohol oramine or water; and ring closure reactions of functional unsaturatedcompounds such as unsaturated amides with CO. The unsaturated organicreactants are preferably olefinically unsaturated compounds, morepreferably olefinic hydrocarbons.

The most preferred carbonylation is the improved, selectivehydroformylation process of the present invention, however, the novelcomplexes of the invention can be employed as catalysts in other priorart methods to obtain good results.

The most preferred carbonylation is an improved, selectivehydroformylation comprising reacting an olefin with a mixture of carbonmonoxide and hydrogen in the presence of an alkyl diaryl phosphinehalogen free rhodium complex as a catalyst to produce mainly analdehyde, preferably via carbonylation at the less substituted vinyliccarbon. Halogen free means that there is no reactive halogen,particularly chlorine, bonded to rhodium.

An improved method for hydroformylation was discovered comprisingreacting an olefin with CO and H₂ in the presence of a tris- andbis-(alkyl diaryl phosphine) rhodium carbonyl complex catalyst free fromhalogen on the rhodium and excess free tertiary phosphine ligand whereinsaid improvement is effected by an appropriately high ratio of both H₂/CO and ligand/Rh to produce a selective catalyst system of improvedthermal stability and long term operational stability which leads to aratio above four of n- and i-aldehyde primary products said productsbeing the major primary products when the method employs a 1-n-olefin asstarting reactant.

The preferred complex catalysts are nonchelating tris-(substituted alkyldiaryl phosphine) rhodium carbonyl hydride complex compounds of theformula:

    [Ar.sub.2 P(CH.sub.2).sub.m ER.sub.y "'].sub.3 Rh(CO)H

wherein the meaning of the symbols is as previously defined, except ER"'is a nonchelating heteroorganic radical, preferably being selected fromthe group consisting of silane silicone; ether, ester, keto and hydroxyoxygen; phosphine, phosphonium and phosphorus ester phosphorus; amine,amido, heterocyclic and ammonium nitrogen; sulfide and sulfone sulfur.

In hydroformylation reactions employing the novel complexes of theinvention, organic nonhydrocarbon solvents, preferably of weak,nonsubstituting ligand character, are advantageously used. Preferredsolvents of ligand character are triaryl phosphines, such as triphenylphosphine, triaryl stibines, triaryl arsines. Other preferred organicsolvents are ketones such as acetophenone, diphenyl ketone, polyethyleneglycol and organic silicone compounds such as diphenyl dipropyl silane.More preferred ligand solvents are triaryl phosphines. Of course, themost preferred solvent is one used in the process of the presentinvention as described above containing an excess of an alkyl phosphineligand, preferably the same alkyl diaryl ligand as complexed with the(RhX_(n))_(s) group. This last reaction system has been found to provideparticularly advantageous results as explained in the following.

As far as other prior art carbonylation processes employing the presentnovel complexes are concerned such processes can be performedadvantageously under the usual conditions such as those described in theearlier referenced Falbe monograph. Generally, the olefins describedabove can be employed in processes using the novel complexes of theinvention. However, prior art processes employing the novel catalystswill normally have to be performed at higher temperature becausealthough the novel complexes have greater stability and selectivity thantriaryl phosphine complexes previously employed, the novel complexesgenerally provide relatively lower reaction rates. Typical totalpressures, rhodium concentrations, ligand concentration and H₂ to COpartial pressure ratios for such prior art processes are

Total pressure: 30 to 30,000 psi

Rh concentration: 10 to 10000 ppm

Ligand concentration: 100 to 200,000 ppm

Moreover, in contrast to the process of the present invention, theseprior art processes can employ an excess of any tertiary phosphine,including triphenyl phosphine. However, if the excess ligands includephosphines having structures other than that of the complexed diarylalkyl phosphine, such ligand should not displace more than one of thethree ligands of the novel tris-(diaryl alkyl phosphine) rhodium complexof the invention. The other complexing groups present in substitutedalkyl diaryl phosphines should not effect such a multiple substitutioneither.

The novel complexes of the invention can also be employed in combinedprocesses such as a combined hydroformylation/aldolization. For example,a process employing the normal prior art hydroformylation conditiondiscussed above along with an aldol condensation catalyst and a novelcomplex of the invention would be one such process.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 shows the key steps in the mechanism of phosphine-rhodium complexcatalyzed hydroformylation of olefins.

FIG. 2 illustrates a comparative ³¹ P NMR spectra of certain rhodiumcomplexes.

FIG. 3 illustrates a ³¹ P NMR study of certain ligand exchange rates asa function of temperature.

FIG. 4 is a schematic representation of an autoclave forhydroformylation.

FIG. 5A is a graphical comparison of certain catayst stabilities at hightemperature hydroformylation of butene-1.

FIG. 5B is a graphical comparison of certain catalyst stabilities at lowligand/Rh ratio in Hydroformylation of butene-1.

FIG. 6 is a graphical representation of butene hydroformylation rateversus temperature correlations in the presence of SEP and TPP basedrhodium-phosphine complex catalysts.

FIG. 7 is a graphical representation of 1-butene hydroformylationtemperature versus n-valeraldehyde (n) to total valeraldehyde (n+i)ratio correlations in the presence of SEP and TPP basedrhodium-phosphine complex catalysts.

FIG. 8 is a graphical representation of 1-butene hydroformylationtemperature versus butane by-product formation correlations in thepresence of SEP and TPP based complex catalysts.

FIG. 9 is a graphical representation of 1-butene hydroformylationtemperature versus 2-butenes by-product formation correlations in thepresence of SEP and TPP complex catalysts.

FIG. 10 is a graphical representation of the effect of SEP ligand torhodium ratio on selectivity of butene hydroformulation at 145° and 170°C.

FIG. 11 is a graphic representation of the effect of carbon monoxidepressure on ratio of n-valeraldehyde (n) to total valeraldehyde (n+i)product of 1-butene hydroformylation.

FIG. 12 is a graphical representation of aldehyde production rate duringcontinuous butene hydroformylation.

BEST MODE OF CARRYING OUT THE INVENTION

In accordance with another aspect of the present invention, it has alsobeen discovered that diaryl alkyl phosphine complexed catalysts can beemployed in a new hydroformylation process for the production ofaldehydes from olefinic compounds and that highly advantageous resultscan be obtained thereby. Thus, the process of the present inventioncomprises reacting the olefinic compound with hydrogen and carbonmonoxide in the presence of a reactive mixture comprising (1) arhodium-containing catalyst having no reactive halogen and having atleast one ligand complexed with said rhodium, wherein the complexedligand comprises a complexed compound containing at least one diarylphosphino alkyl group and wherein the number of such diaryl phosphinoalkyl groups in complex association with said rhodium is at least two,and (2) a non-complexed ligand substantially all of which is anon-complexed compound containing at least one diaryl phosphino alkylgroup, wherein the molar ratio of the non-complexed ligand to rhodium isgreater than 100 and wherein the ratio of the partial pressures ofhydrogen to carbon monoxide is at least 3:1.

The most preferred carbonylation is an improved, selectivehydroformylation comprising reacting an olefin with a mixture of carbonmonoxide and hydrogen in the presence of an alkyl diaryl phosphinehalogen free rhodium complex as a catalyst to produce mainly analdehyde, preferably via carbonylation at the less substituted vinyliccarbon. Halogen free means that there is no reactive halogen,particularly chlorine, bonded to rhodium.

An improved method for hydroformylation was discovered comprisingreacting an olefin with CO and H₂ in the presence of a tris- andbis-(alkyl diaryl phosphine) rhodium carbonyl complex catalyst free fromhalogen on the rhodium and excess free tertiary phosphine ligand whereinsaid improvement is effected by an appropriately high ratio of both H₂/CO and ligand/Rh to produce an improved stability which leads to aratio above four of n- and i-aldehyde primary products said productsbeing the major primary products when the method employs a 1-n-olefin asstarting reactant.

The preferred complex catalysts are nonchelating tris-(substituted alkyldiaryl phosphine) rhodium carbonyl hydride complex compounds of theformula

    [Ar.sub.2 P(CH.sub.2).sub.m ER"'].sub.3 Rh(CO)H

wherein the meaning of the symbols is as previously defined, except ER"'is a nonchelating heteroorganic radical, preferably being selected fromthe group consisting of silane silicone; ether, ester, keto and hydroxyoxygen; phosphine, phosphonium and phosphorus ester phosphorus; amine,amido, heterocyclic and ammonium nitrogen; sulfide and sulfone sulfur.

As stated, such selective reactions were unexpectedly found to dependcritically on the alkyl diaryl phosphine complex catalysts, the excessof phosphine ligand and the ratio of H₂ /CO synthesis gas reactant,i.e., the CO partial pressure. The selectivity also depends on the typeof olefin employed. In an important embodiment of the new proces, theprocess is run on a continuous basis with the reaction being conductedat a temperature, olefin, H₂ and CO feed rates, a rhodium concentrationand a rhodium to non-complexed ligand molar ratio effective to provide arate of production of said aldehydes of at least about 0.1 g mole/l-hr,and wherein the ratio of the partial pressures of hydrogen to carbonmonoxide is at least 3:1; and the aldehyde product is continuouslyremoved as a vapor from the reaction mixture. Each of theabove-described processes is hereinafter described as the process of theinvention. In these processes, the CO partial pressure is preferablykept low, e.g., below 100 psi.

The process of the present invention has been found to provide acatalyst system having good thermal stability. Moreover, in the presenceof a large excess of the diaryl alkyl phosphine ligand, the catalystactivity was surprisingly maintained while stability was increased. Theprocess of the present invention was also found to provide unexpectedlygood selectivity for producing n-aldehyde products from alpha-olefins.

In a preferred embodiment of the process of the present invention, theolefinic carbon compound is one containing an alpha-olefinic doublebond. In this preferred process, the H₂ /CO ratio and the amount of thenon-complexed compound containing at least one diaryl phosphino alkylgroup are effective to provide an aldehyde product having a normal toiso isomer ratio of at least about 4:1. Again, it is preferable tomaintain a low CO partial pressure.

In another embodiment of the process of the present invention, thereaction is preferably conducted at a temperature of at least about 90°C., a rhodium concentration of at least about 0.0001 molar and anon-complexed ligand to rhodium molar ratio of over 100. Also, thenon-complexed ligand present in the reaction mixture preferably consistsessentially of the non-complexed compound containing at least one diarylphosphino alkyl group.

In yet another preferred embodiment of the process of the presentinvention, the L/Rh ratio, i.e., of the non-complexed compoundcontaining at least one diaryl phosphino alkyl group to rhodium, ispreferably above 120, more preferably above 240, and most preferablyabove 400. By raising the ligand to rhodium ratio when alpha-olefins areused in the process of the invention, higher normal to iso isomer ratiosof the aldehyde product are obtained and accordingly, higher ligand torhodium ratios are preferred in such cases. In a particularly preferredembodiment of the invention, the non-complexed ligand present during thereaction consists essentially of the non-complexed compound containingat least one diaryl phosphino alkyl group, and this ligand is present ina molar ratio, i.e., L/Rh of greater than 100.

Suitable complexed and non-complexed compounds containing at least onediaryl phosphino alkyl groups for use in the process of the inventioninclude compounds of the following formula (which includes known diarylalkyl phosphines as well as the novel substituted diaryl phosphino alkylcompounds which are exemplified by Formula I):

    (Ar.sub.2 PQ).sub.b E.sup.y R.sub.y-b

wherein Ar is an aryl group containing from 6 to 10 carbon atoms;

Q is a divalent organic radical selected from an alkylene radical and analkylene radical the carbon chain of which is interrupted with eitheroxygen or phenylene groups, wherein the alkylene radical contains from 2to 30 carbon atoms;

E represents a member selected from a covalent bond, ##STR26## --O-- and--S--, wherein R¹, R² and R³ are each alkyl groups containing from 1 to30 carbon atoms, wherein R⁹ is a member selected from H, an alkyl groupcontaining from 1 to 30 carbon atoms and an aryl group containing from 6to 10 carbon atoms, and wherein X is an integer of 0 or 1 with theproviso that at least one x is 1;

y represents the valence bonds of the group E available for bonding tothe groups Q and R (Thus, for a covalent bond, y is 2; for --Si--, y is4; and for ##STR27## y is 3.);

each R group independently represents a member selected from an alkylgroup containing from 1 to 30 carbon atoms and an aryl group containingfrom 6 to 10 carbon atoms, and when E is --N<, R also represents amember selected from ##STR28## which member together with the N atomforms a heterocyclic ring, wherein R⁴, R⁵, R⁶, R⁷ and R⁸ are hydrocarbylradicals such that the heterocyclic ring contains from 5 to 6 atoms;

and b is an integer of from 1 to 4, provided that y-b is not less thanzero. Preferably, the complexed and non-complexed compounds containingdiaryl phosphino groups are of the formula

    Ar.sub.2 PQE.sup.y R.sub.y-1

wherein Ar, Q, E, Y and R are as defined above.

Suitable complexed and non-complexed compounds containing diarylphosphino alkyl groups which can be used in the process of the presentinvention include the known diaryl phosphino alkyl compounds discussedabove in the section of the present specification entitled Background ofthe Invention, the tetraalkyl phosphonium substituted phosphine ligandsdisclosed in the U.S. Application entitled "Tetraalkyl PhosphoniumSubstituted Phospine and Amine Transition Metal Complexes and ProcessesFor Use Thereof" filed on Jan. 23, 1980, now U.S. Pat. No. 4,302,401, inthe name of Alexis A. Oswald, and the ligands of our novel catalystsdiscussed in detail above (i.e., of Formula I).

Non-chelating ligands of the formula

    Ar.sub.2 P(CH.sub.2).sub.m PAr.sub.2

wherein Ar is aryl as defined above and m is an integer of from 4 to 14,represent yet another class of suitable complexed and non-complexedligands.

The tetraalkyl phosphonium compounds as mentioned above represent stillanother class of ligands suitable for use in the process of the presentinvention. These phosphonium derivatives can be exemplified by thegeneral formula

    (Ar.sub.2 PQ)P.sup.+ R.sup.1 R.sub.2 R.sup.3 Z.sup.-

wherein Ar, Q, R¹, R² and R³ are as defined above and Z⁻ represents ananion. The Z⁻ anion electrically neutralizes the ligand moiety; can bemonovalent or polyvalent and is preferably a non-coordinating anion.Examples of suitable Z anions include halide, hydroxide, sulfate,sulfonate, phosphate, phosphonate, phosphite, tetraphenyl boride,fluorophosphate, carboxylate such as acetate, phenoxide and alkoxide. Aparticularly preferred subclass of such phosphonium ligands is of theformula

    Ph.sub.2 P--CH.sub.2 --.sub.m P.sup.+ R.sup.1 R.sup.2 R.sup.3 Z

wherein m is an integer of from 1 to 30 and the other symbols are asdefined above. These phosphonium ligands are also employed in complexassociation with rhodium as catalyst suitable for use in the process ofthe present invention.

Specific examples of such complexed and non-complexed compoundscontaining diaryl phosphino alkyl groups include ethyl diphenylphosphine, propyl diphenyl phosphine, butyl diphenyl phosphine, Ph₂ PCH₂CH₂ Ph, ##STR29## Ph₂ PCH₂ CH₂ Si(CH₃)₃, Ph₂ PCH₂ CH₂ C(CH₃)₃, and Ph₂PCH₂ C(CH₃)₃, wherein Ph here and through this specification andattached claims represents phenyl.

In yet another embodiment of the process of the present invention therhodium-containing catalyst employed is of the general formula

    [(Ar.sub.2 PQ).sub.b E.sup.y R.sub.b-y ].sub.g.(RhX.sub.n).sub.s

wherein Ar, Q, y, E, R and b are as defined above, X is an anion ororganic ligand, excluding halogen, satisfying the coordination sites ofthe rhodium metal; g times b is 1 to 6; n is 2 to 6; and s is 1 to 3.Other preferred catalysts for use in the process of the presentinvention include rhodium-containing catalysts of the formulae:

    [(Ar.sub.2 PQ).sub.b E.sup.y R.sub.y-b ].sub.g.[RhH(CO)].sub.s

and

    (Ar.sub.2 PQE.sup.y R.sub.y-1).sub.3 RhH(CO)

wherein Ar, Q, E, y, R, b, g and s are as defined above.

A preferred class of complexes suitable for use in the process of thepresent invention include complexes of the formula

    (Ar.sub.2 PQE.sup.y R.sub.y-1).sub.3 Rh(CO)H

and

    [(Ar.sub.2 PQ).sub.b E.sup.y R.sub.y-b ].sub.g [Rh(CO)H].sub.s

wherein E represents a covalent bond or ##STR30## R is an alkyl group,preferably a substituted or unsubstituted alkyl group containing 1 to 30carbon atoms and more preferably a saturated open chain alkyl group; andAr, Q, y and b are as defined above. Particularly suitable compoundswithin this class include compounds of the formula

    [Ar.sub.2 P--CH.sub.2 --.sub.m R].sub.3 Rh(CO)H

wherein m is an integer of from 1 to 30, preferably from 2 to 22 andmore preferably from 2 to 4; R is a straight-chain, branched or cyclicalkyl group or an aryl group such as isopropyl, tertiary butyl,cyclohexyl, or phenyl. A particularly suitable catalyst for use in theprocess of the present invention is

    (Ph.sub.2 PCH.sub.2 CH.sub.2 CH.sub.3).sub.3 Rh(CO)H.

Other examples of suitable catalysts for use in the present inventioninclude Rh(CO)H(Ph₂ PCH₂ CH₂ Ph)₃, ##STR31## Rh(CO)H(Ph₂ PCH₂ CH₂Si(CH₃)₃)₃, Rh(CO)H(Ph₂ PCH₂ CH₂ C(CH₃)₃)₃, and Rh(CO)H(Ph₂ PCH₂C(CH₃)₃)₃.

The Ar, Q and R groups in the above-discussed ligands and complexesthereof can also be substituted with various substitutent groups. Ingeneral, the substitutents on the Ar, Q and R groups, and for thatmatter any substituent in the ligands and complexes used in the processof the present invention or in the novel complexes of the invention asset forth above in Formula I, are those which are chemically unreactivewith the reactants used in and the products of the desired catalyzedreaction, e.g., a hydroformylation reaction. The same exemplarysubstituents can be used on any of the Ar, Q and/or R groups. Suitablesubstituents include halogen, carboxy, phenoxy, and hydroxy groups andalso alkyl, alkoxy, acyl, acyloxy, acylamide, carbamido andcarbohydrocarbyloxy groups containing from 1 to 30 carbon atoms, andpreferably from 1 to 12 carbon atoms.

Suitable Ar groups for use in the complexed and non-complexed compoundsor rhodium complexes thereof include aryl groups containing from 6 to 10carbon atoms. The terminology "aryl group containing from 6 to 10 carbonatoms", as used in this specification and in the attached claims, ismeant to include aromatic groups containing from 6 to 10 carbon atoms inthe basic aromatic structure which structure can be substituted with anychemically unreactive substituent as discussed above. The aryl groupsare also intended to include heterocyclic aromatic groups such aspyrryl, thienyl and furyl. The substituents on the aryl group, if any,are preferably bound to a phenyl group. Mono- and di-substituted phenylgroups are preferred. Thus, examples of suitable aromatic groups includephenyl, fluorophenyl, difluorophenyl, tolyl, xylyl, benzoyloxyphenyl,carboethoxyphenyl, acetylphenyl, ethoxyphenyl, phenoxyphenyl, biphenyl,naphthyl, hydroxyphenyl, carboxyphenyl, trifluoromethylphenyl,tetrahydronaphthyl, furyl, pyrryl, thienyl, methoxyethylphenyl,acetamidophenyl, and dimethylcarbamylphenyl.

Q in the above formulas represents a divalent organic radical selectedfrom an alkyl group and an alkylene group the carbon chain of which isinterrupted with ether oxygen or phenylene groups, wherein the alkylenegroup contains from 1 to 30 carbon atoms, preferably from 2 to 22 carbonatoms, and more preferably from 2 to 4 carbon atoms. The terminology"alkylene group", as used in this specification and in the attachedclaims, is meant to include an alkylene group containing 1 to 30 carbonatoms in the basic alkylene structure, which structure may again besubstituted with any chemically unreactive substituent as discussedabove. Examples of suitable Q organic radicals include ethylene,trimethylene, butylene, decamethylene, docosamethylene,tricontamethylene, phenyl bis(ethyl), ethylene bis-(oxyethyl),ethylene-bis oligo(oxyethyl), oxy ethyl propyl, oxy ethylperfluoroethyl, oxy ethyl hydroxypropyl, xylylene and octadecamethylene.Preferably Q represents --CH₂ --_(m) wherein m ranges from 1 to 30,preferably from 2 to 14, and most preferably from 2 to 4.

Suitable R groups for use in the above compounds include aryl groupscontaining from 6 to 10 carbon atoms and alkyl groups containing from 1to 30 carbon atoms and when E is --N<, R can also represent a memberselected from ##STR32## which member together with the N atom forms aheterocyclic ring, wherein R⁴, R⁵, R⁶, R⁷ and R⁸ are hydrocarbylradicals such that the heterocyclic ring contains from 5 to 6 atoms.These R groups may again be substituted with substituents that arechemically unreactive as discussed above. Suitable R aryl groups includeany of those mentioned above in the definition of suitable Ar groups. Bythe terminology "alkyl group containing from 1 to 30 carbon atoms", wemean to include alkyl groups containing from 1 to 30 carbon atoms in thebasic alkyl structure, which can be straight-chain, branched or cyclicand which can be substituted with any chemically unreactive substituentas discussed above. The alkyl groups are preferably primary or secondaryalkyl groups, more preferably primary alkyl groups containing from 2 to22 carbon atoms, and even more preferably from 6 to 14 carbon atoms.Exemplary alkyl groups include methyl, ethyl, propyl, n-butyl,iso-butyl, t-butyl, n-hexyl, cyclohexyl, methylcyclopentyl, isopropyl,decyl, fluoropropyl, docosyl, triacontyl, cyclopentyl, phenyl,methoxyethoxyethyl, acetylethyl, tris-hydroxy substituted t-butylethyl,triphenylmethylethyl, hydroxypropyl, carbomethoxyethyl, phenoxyethyl,benzamidoethyl, benzoyloxyethyl, pyrrylethyl, furylethyl andthienylethyl.

X in the above formulae represents an anion or organic ligand whichsatisfies the coordination sites of the rhodium metal, preferably anon-coordinating anion. Suitable X groups include H⁻, alkyl⁻, aryl⁻,substituted aryl⁻, CR₃ ⁻, C₂ F₅ ⁻, CN⁻, N₃ ⁻, COR⁻, PR₄ ⁻, (where R isalkyl or aryl), carboxylate such as acetate, acetylacetonate, SO₄ ²⁻,sulfonate, NO₂ ⁻, NO₃ ⁻, O₂ ⁻, CH₃ O⁻, CH₂.sup.═ CHCH₂ ⁻, CO, C₆ H₅ CN,CH₃ CN, NO, NH₃, pyridine, (C₄ H₉)₃ P, (C₂ H₅)₃ N, chelating olefins,diolefins and triolefins, tetrahydrofuran, CH₃ CN, and triphenylphosphine. Preferred organic ligands are readily displaceable such ascarbonyl, olefins, tetrahydrofuran and acetonitrile. The most preferredX ligands are CO and H.

The preferred olefin reactants for use in the hydroformylation processof the present invention and other hydroformylation processes employingthe novel complexes of the present invention are ethylene and its mono-and disubstituted derivatives. The formula of the preferred compounds isshown in the following representation of the hydroformylation reaction:##STR33## wherein T¹, T² and T³ are independently selected from hydrogenand organic radicals containing from 1 to 1000 carbon atoms, preferablyfrom 1 to 40 carbon atoms, more preferably from 1 to 12 carbon atoms,and most preferably from 4 to 6 carbon atoms, with the proviso that atleast one of T¹, T² or T³ be hydrogen. These radicals can beunsubstituted or substituted, but preferably they are unsubstituted.

As such, the preferred olefins include symmetrically disubstituted,i.e., internal, olefins of the formula

    T.sup.3 --CH═CH--T.sup.2

wherein the meanings of T³ and T² in this case is the same as aboveexcept that they exclude H. Other, particularly preferred olefins aremono- and disubstituted unsymmetrical olefins of the formula ##STR34##wherein the meaning of T¹ and T² in this case also excludes hydrogen.The monosubstutited olefins are particularly preferred. Suchspecifically preferred olefins are propylene, 1-butene, 1-pentene,1-hexene, 1-heptene, 1-octene. The unsubstituted parent compound,ethylene, is also a specifically preferred reactant.

As far as the terminal versus internal attack of unsymmetricallysubstituted olefins is concerned, the disubstituted compound is a highlyspecific reagent in hydroformylation. It leads to mostly terminal orso-called n-aldehydes: ##STR35## Specifically, preferred reagents ofthis type are isobutene, 2-methylbutene, 2-methylpentene, 2-ethylhexene.

In contrast to these disubstituted alpha-olefins, the selectivity of thehydroformylation of unsymmetrically monosubstituted olefins in theprocess of the present invention and other processes employing our novelcomplexes as set forth and fully explained further below depends on theexcess phosphine concentration and CO partial pressure. The preferredcourse of the reaction is via terminal attack on the olefin to producethe corresponding n- rather than i-aldehydes: ##STR36## The size, i.e.,steric demand of the T¹ substituent, also affects the selectivity. Inthe case of propylene, having the small methyl group for T¹, theselectivity to the n-product is relatively small. 1-Butene, with ethylfor T¹, is hydroformylated with surprisingly higher selectivity.3-Methyl-1-butene, where T¹ equals i-propyl, reacts even much moreselectively. Apparently, the bulkier and more branched T¹ groups hinderthe attack on the internal, beta-vinylic carbon. The preferredmonosubstituted olefins are n-1-olefins, wherein T¹ is n-alkyl.Particularly preferred reactants are 1-butene and propylene.

Exemplary olefinic reactants for use in the process of the presentinvention can be of open chain or cyclic structure. There can be amultiplicity of double bonds present in the higher molecular weightreactants. However, diolefin and polyolefin reactants of nonconjugatedcharacter are preferred. The saturated carbon atoms of these olefins canhave non-hydrocarbon substituents such as hydroxy, carbonyl,carboxylate, ester, alkoxide, acetal and fluorine groups. Of course,these substituents must not react with the components or the products ofthe hydroformylation reaction systems. Suitable cyclic olefins orolefins having a multiplicity of double bonds include 1-hexadecene,3-hexene, cyclohexene, 1,7-octadiene, 1,5-cyclododecadiene, methylcyclopentene, 1-tricosene, 1,4-polybutadiene, methyl oleate, ethyl10-undecanoate, 3-butenyl acetate, diallyl ether, allyl fluorobenzene,6-hydroxyhexene, 1-hexenyl acetate, 7-heptenyl diethyl acetal,norbornene, dicyclopentadiene, methylene norbornene, trivinylcyclohexane, allyl alcohol.

While we do not wish to be limited by any theory by which the process ofthe invention and our novel complexes work, it is believed that insolution and particularly under reaction conditions, both the tris- andbis-phosphine rhodium complexes are present. It was found via ³¹ P nmrstudies that the widely accepted equilibration mechanism of tris- andbis-phosphine rhodium carbonylhydride complexes occurs according to thereaction formula: ##STR37## The overall mechanism of hydroformylationcatalysis of the present complexes is shown by FIG. 1. In FIG. 3, thereis shown a side-by-side comparison of the ³¹ P nmr spectra at 30°, 60°and 90° C. for solutions containing, on the one hand, (Ph₃ P)₃ Rh(CO)Hand Ph₃ P (TPP) as excess ligand, and on the other hand, containing (Ph₃P)₃ Rh(CO)H and excess Ph₂ PCH₂ CH₂ Si(CH₃)₃ ligand (SEP ligand) asstarting materials.

Equilibration of the stable tris-phosphine complex to provide some ofthe highly reactive, coordinatively unsaturated trans-bis-phosphine isto occur in an active catalytic system. However, in the case of stablecatalysts, most of the rhodium is present in the stable tris-phosphinecomplex form.

FIG. 3 also shows that the line shapes of the signals of the 30° C.spectra of both systems showed little signal broadening in both cases.This indicated comparably slow exchange rates of about 25 per second. Inalternative terms, relatively long average exchange lifetimes, in theorder of 2×10⁻² sec, were indicated for both complex systems tested. At60° C., considerable line broadening occurred, indicating a much fasterexchange. The exchange acceleration was greater in the case of theexcess triphenyl phosphine ligand system (k=600 vs. 80), indicating anaverage lifetime of about 3×10⁻³ sec for the excess triphenyl phosphineligand system and of about 6×10⁻³ sec for the excess trimethylsilylethyldiphenyl phosphine ligand system. At 90° C., only a single, broad signalcould be observed for the excess triphenyl phosphine ligand system,while the excess trimethylsilylethyl diphenyl phosphine ligand systemstill exhibited separate, although extremely broad, chemical shiftranges for the complexed and free phosphorus species. Apparently, theexchange acceleration in the case of the excess triphenyl phosphineligand system was tremendous at 90° C. with the average lifetime betweenexchanges being reduced by about two orders of magnitude to 5×10⁻⁵ sec(k=10,000). In the case of the excess trimethylsilylethyl diphenylphosphine ligand system, the average lifetime dropped by about one orderto 5×10⁻⁴ sec (k=1,500). It must be emphasized that the exchange ratesand lifetimes may change somewhat when the lineshape is subjected to arigorous computer analysis. The relative order of their values willremain unaltered, however.

It is interesting to note that there was no great change of equilibriawith the increasing exchange rates. Apparently, both ligand eliminationand addition increase similarly in this temperature range. Thetris-phosphine rhodium species remained the dominant form of complexes.However, in the triphenyl phosphine complex system including free excesstrimethylsilylethyl diphenyl phosphine ligand, the rhodium predominantlycomplexed with the SEP ligand.

The role of excess phosphine ligand is apparently to maintain theequilibria in favor of the tris-phosphine complex, i.e., to reduce boththe concentration and average lifetime of the unstable and highlyreactive bis-phosphine complex. The increased ligand exchange rateprovides enough active bis-phosphine complex catalytic species for fasthydroformylation, without leading to non-catalytic side reactions, i.e.,catalyst decomposition.

Our comparative ³¹ P nmr studies of the known TPP catalyst plus excessTPP ligand system showed that it has a mechanism similar to that of theSEP system of the invention; however, the thermal activation andcatalyst destabilization of the TPP system occurs at lower temperaturesthan for the SEP system. In other words, the tris-(alkyl diarylphosphine) rhodium carbonyl hydride plus excess alkyl diarylphosphine-based systems of the present invention are surprisinglyimproved high temperature hydroformylation catalysis systems.

The results of ³¹ P nmr studies of tris-phosphine rhodium complexformation where also correlated with catalyst activity. It was foundthat those alkyl diphenyl phosphines which do not form trio-phosphinecomplexes for steric reasons are not suitable ligands for the presentselective catalysts. Also, it was found that substitution of thealpha-carbon and multiple substitution of the beta-carbon of the Qalkylene group and o,o'-substitutions of the Ar aryl groups of theligands used in the process of the present invention generally interferewith the complexation, i.e., the desired catalyst formation.

Common five and six membered chelate type complexes of alkylenebis-phosphines, e.g., ##STR38## are not acceptable selective catalystligands either according to the concept of the process of the presentinvention, because they form bis-phosphine complexes of cis- rather thantrans-configuration.

In the process of the present invention, substantially all of the excessphosphine ligand is an alkyl diaryl phosphine, preferably a phosphineligand identical with that of the complex. Preferably, from about 1 to90% by weight of the excess phosphine ligand is a diaryl alkyl phosphineand more preferably from about 5 to 50% by weight is a diaryl alkylphosphine. In another preferred embodiment, the excess phosphine ligandconsists essentially of an alkyl diaryl phosphine. By the terminology"consists essentially of" as used in this specification and in theclaims attached hereto, we mean that only small amounts of non-diarylalkyl phosphine ligand are present which will not affect the stabilityand selectivity of the catalyst system, e.g., such amount as might bepresent by forming the rhodium complex in situ starting withtris-(triphenyl phosphine) carbonyl hydrido rhodium complex and, as thesole excess ligand, a diaryl alkyl phosphine such as SEP or diphenylpropyl phosphine.

The rhodium complex catalysts are obviously very expensive due to thehigh cost of rhodium. As such, in the process of the present inventionand in other processes employing the novel rhodium complexes of theinvention, the rhodium complex concentration is to be carefully selectedto be most effective on a rhodium basis. Of course, a catalyticallyeffective amount of the rhodium will be present.

The preferred concentration of the rhodium complex as used in theprocess of the present invention and in other processes employing thenovel rhodium complexes of the invention is in the range of 1×10⁻⁶ to1×10⁻¹ mole of rhodium per mole of olefin reactant. More preferredconcentrations are in the range of 1×10⁻⁵ to 1×10⁻¹ mole of rhodium permole of olefin and the most preferred range is 1×10⁻⁴ to 1×10⁻² mole ofrhodium per mole of olefin. Thus, the preferred rhodium concentration isnormally in the range of from 10 to 1000 ppm. However, the preferredcatalyst concentrations are directly affected by the concentration offree ligand present, especially the excess diaryl alkyl phosphineligand. Since the excess phosphine reduces the concentration of theactive bis-phosphine complexes, a larger excess reduces theeffectiveness of the total rhodium complex present. The higher theligand concentration, the higher the rhodium level required for acertain reaction rate. Nevertheless, a high phosphine concentration isemployed in the process of the invention to achieve the desired catalyststability and selectivity.

In the process of the invention, the minimum weight percent amount ofexcess ligand in the reaction medium is preferably about 1 wt.%, morepreferably 5 wt.%. However, in general, the phosphine concentration islimited to 50 wt.% of the reaction mixture. At an appropriate rhodiumconcentration, the reaction can be carried out using the excess diarylalkyl phosphine as the solvent. Sufficient excess diaryl alkyl phosphineconcentration is used in the preferred process to carry out the reactionat the desired temperature under the desired conditions with the desiredselectivity and activity maintenance. The rhodium complex concentrationcan then be adjusted to achieve the desired reaction rate.

Due to the interdependence of the alkyl diaryl phosphine rhodium complexand the excess phosphine ligand in the process of the invention, themole ratio of diaryl alkyl phosphine ligand to mole equivalent rhodiumcomplex, L/Rh, is preferably in the range of from about 40 to about3000. The L/Rh ratio is preferably above 120, more preferably about 240,most preferably above 400. In general, higher ratios are selected whenthe desired operation is a continuous rather than a batchwise operation.

The selectivity of the process of the present invention is alsodependent on the molar ratio of gaseous CO and H₂ reactants. This H₂ /COratio should be greater than 3:1 preferably in the range of 200:1 to 3:1and more preferably, from 100:1 to 5.5:1 and most preferably from 20:1to 10:1.

The present process of the invention is also operated at surprisinglylow pressures, but can be operated at pressures of from 1 to 10,000 psi.The preferred pressures are between about 1 and 1000 psi, i.e., about 1and 68 atm. It is more preferred to operate between about 25 and 500psi, i.e., about 2 and 34 atm.

Some of the above pressure limitations are due to the sensitivity of thepresent rhodium complex catalyst to the partial pressure of CO. Thetotal partial pressure of CO is preferably less than about 200 psi(approximately 8 atm.), more preferably less than about 100 psi, andmost preferably less than about 50 psi. If the CO partial pressure istoo high, the catalyst complex is deactivated due to the formation ofcarbonyl derivatives.

In the process of the present invention, the partial pressure ofhydrogen has no critical upper limit from the viewpoint ofhydroformylation. Nevertheless, the preferred partial pressure ofhydrogen is between about 50 and 500 psi, i.e., 4 and 34 atm. Above acertain partial pressure of hydrogen, the relative rates of competinghydrogenation and isomerization reactions suddenly increase, which is tobe avoided in the process of the present invention. However, if suchhydrogenation and isomerization reactions are desired, the novelcomplexes of the invention are surprisingly active hydrogenation andisomerization catalysts. In the latter case, the rhodium complex of theinvention becomes a multifunctional catalyst when the H₂ /CO ratio istoo high and/or the CO concentration is insufficient.

When working with a terminal olefin, the selectivity to paraffin andinternal olefin was sometimes significantly increased for the abovereasons. For example, the reaction of 1-butene led not only to n- andi-valeraldehydes, but also to significant amounts of n-butane and cis-and trans-2-butenes. This effect of high hydrogen partial pressuresbecomes particularly critical under non-equilibrium conditions where thesystem is starved of CO. In such a case, practically only the n-aldehydeplus by-products are formed. In a preferred mode of operation, theoptimum combination of reaction parameters is maintained by assuringequilibrium conditions by appropriate reactant introduction and mixing.

In the upper temperature range of the process of the invention, asignificant part of the total pressure can be maintained by either avolatile reactive or unreactive olefin or a saturated, aliphatic oraromatic hydrocarbon or by an inert gas. This preferred mode ofoperation allows a limitation of synthesis gas pressure, while assuringa higher solubility of the gaseous reactants in the liquid reactionmixture.

The operation of the process of the invention can be optimized in asurprisingly broad temperature range. The range of temperature ispreferably between 50° and 200° C., more preferably, between 90° and175° C., and most preferably, between 120° and 150° C. Compared to priorart catalyst systems employing triphenyl phosphine, the maintenance ofthe catalyst activity and selectivity at the higher temperatures in theprocess of the present invention is particularly unique. High rates ofselective hydroformylation of alpha-n-olefins can be realized andmaintained to high conversion at 145° C. when using the present processconditions.

The process of the invention can be carried out either in the liquid orin the gaseous state. The catalyst can be employed as such eitherdissolved in the liquid reaction medium or deposited on a suitable solidsuch as silica or alumina. The preferred process employs a liquid, morepreferably homogeneous liquid, reaction phase with the catalyst systemdissolved, i.e., homogeneous catalyst.

The preferred homogeneous catalysis process of the invention is affectedby the solvents used although a large variety of organic solvents isemployable. In general, the more polar solvents of higher dielectricconstant are increasingly preferred as long as they possess sufficientsolvent power for the olefin reactant and do not interfere with thestability of the desired catalyst complex species. As such, aromatichydrocarbons are suitable solvents, although organic nonhydrocarbonsolvents are preferably used. More preferably, the latter are of a weaknon-substituting ligand character. As such, oxygenated solvents are mostpreferred.

Preferred solvents include those of ligand character, e.g., diaryl alkylphosphine, or organic solvents, e.g., ketones such as acetophenone,diphenyl ketone; polyethylene glycol; organic silicone compounds such asdiphenyl dipropyl silane; esters such as 2-ethylhexyl acetate, dipropyladipate, ethylene glycol diacetate; 1,4-butane diol; dimethyl formamide;N-methyl pyrrolidinone 4-hydroxybutyl 2-ethylhexanoate. One of the mostpreferred solvents is an excess of the alkyl diaryl phosphine ligand.

In general, the preferred solvents for the process of the invention,particularly ligands, stabilize the catalyst system and increase itsselectivity, particularly as to the ratio of linear versus branchedproducts. The aldehyde product of the invention is generally anexcellent solvent. Accordingly, the addition of a separate solvent isnot required.

In contrast to the disclosure on the triphenyl phosphine type rhodiumcomplex catalyst system of the previously discussed U.S. Pat. No.4,148,820 by Pruett and Smith, the alkyl diaryl phosphine rhodiumcomplex catalyst systems used in the process of the present inventionand the novel rhodium complexes of the invention are compatible with,i.e., soluble in, a large variety of organic solvents. These solventsinclude the aldehyde trimer condensation products which, according toPruett and Smith, are the only suitable solvents for the triphenylphosphine type based rhodium catalyst system.

Due to the improved stability provided by the process of the presentinvention employing alkyl diaryl phosphine rhodium complex catalysts, acontinuous mode of operation is often advantageous. When using ahomogeneous liquid catalyst system, such an operation can be of acontinuous plug flow type, including a step for catalyst recovery andthen recirculation. The process of the present invention may alsoinvolve a quasi-continuous use of the catalyst employing the cyclicoperation of a unit for hydroformylation and then for product flash-off.Catalyst concentration or other methods of catalyst recovery may involvecomplete or partial recycle. However, a preferred method of operationfor the process of the present invention involves continuous productflashoff.

In the continuous product flashoff process of the present invention, thealdehyde product of the hydroformylation is continuously removed as acomponent of a vapor mixture, while the CO, H₂ and olefin reactants arecontinuously introduced. This process preferably includes therecirculation of most of the unreacted reactants in the gaseous stateand the condensation and thereby removal of most of the aldehyde andaldehyde derivative products. Additional olefin, CO and H₂ are added asrequired to maintain aldehyde production and optimum process parameters.The space velocity of the gas stream is appropriately adjusted andadditional gas purge is used as required to maintain production andcatalyst activity. Since the rhodium complex is not volatile, nocatalyst losses occur. If the diaryl alkyl phosphine ligand is volatile,additional phosphine is added occasionally to maintain its concentrationin the reaction mixture.

During the continuous product flashoff operation, relativelynon-volatile aldehyde oligomers are formed and concentrated in theliquid reaction mixture. The oligomeric hydroxy substituted carboxylicester condensation and redox disproportionation products formed duringpropylene hydroformylation were disclosed in the previously discussedU.S. Pat. No. 4,148,820 of Pruett and Smith. In the present work, it wasfound that analogous derivatives, mainly trimers, are formed during1-butene hydroformylation. The general structure of the isomeric trimersis the following: ##STR39## wherein R is C₂ to C₅, preferably C₃, alkyl.

The above aldehyde trimer is generally the main derivative and atequilibrium conditions of a preferred continuous flashoff process of thepresent invention, it can automatically become the main solventcomponent. When this occurs during 1-butene hydroformylation inaccordance with the process of the present invention, selectivity andproduction rate can be maintained and the concentration of the trimercan be limited to an equilibrium value.

In the continuous product flashoff operation of the process of thepresent invention, carbonylations, especially the hydroformylation ofolefins, are advantageously carried out at a low olefin conversion,preferably at a 20 to 80% olefin conversion. Aldehyde production ratesare preferably between 0.1 and 5 g mole/liter/hour, more preferablybetween 0.5 and 2 g mole/liter/hour. Operating in this manner withoptimized reactant ratios, particularly high linear to branched aldehydeproduct ratios are obtained from alpha-n-olefins.

The continuous process of the present invention can be also employed forthe selective or complete conversion of different types of olefins. Forexample, a mixture of 1- and 2-butenes can be hydroformylated to producemainly n-valeraldehyde and 2-butene. Similarly, a mixture of 1-butene,2-butene and i-butene can be converted selectively to varying degrees.

Using the process of the present invention, the catalysts have improvedthermal stability and thus the application of continuous for batchflashoff processes can be extended to higher olefins leading to aldehydeproducts which are not sufficiently volatile at the normal lowertemperatures used in previous continuous operations. The preferredolefins for continuous product flashoff are of the C₂ and C₆ range andalpha-n-olefin type. 1-Butene and propylene are particularly preferred.

Using the present catalysts of improved thermal stability, theapplication of continuous or batch flashoff processes can be extended tohigher olefins leading to nonvolatile products. The preferred olefinsfor continuous product flashoff are of the C₂ to C₆ range and n-1-olefintype. 1-Butene is a particularly preferred reactant.

In an improved method for continuous hydroformylation, 1-butene isreacted with CO and H₂ in the presence of a tris-(2-trimethylsilylethyldiphenyl phosphine) rhodium carbonyl hydride complex and excess2-trimethylsilylethyl diphenyl phosphine ligand based catalyst systemwherein the reactants are continuously introduced into a liquid reactionmixture comprising dissolved catalyst and ligand and preferably majoramounts of n-valerladehyde trimer, and wherein the aldehyde products arecontinuously removed in the vapor phase, and wherein some of thereactants are recirculated. The improvement is effected by having thecarbon monoxide partial pressure between about 4 and 100 psi, preferablybetween about 80 and 70 psi; the hydrogen partial pressure, preferablybetween about 5 and 500 psi; and the total gas pressure between 25 and500 psi; preferably between 55 and 500 psi; a rhodium complexconcentration between 1×10⁻² and 1×10⁻⁴ mole/liter and phosphine ligandconcentration between 5 and 50 wt. percent, in a temperature rangebetween 80° and 175° C., preferably 110° and 145° C. The aboveconcentrations and temperatures are selected to provide appropriatelyhigh H₂ /CO and Rh/L ratios to constitute an effective catalyst systemin the present continuous operation. Such a system produces 0.5 to 2 gmole/liter/hour aldehyde and loses less than 1%, preferably less than0.3%, of its activity per day while a n/i-aldehyde product ratio inexcess of 9, preferably in excess of 15, is maintained.

The process of the present invention employing alkyl diaryl phosphinerhodium complexes can also be advantageously combined with otherprocesses because of the thermal stability and selectivity of thecatalysis obtained by such processes. The hydroformylation could beadvantageously carried out either when coupled with aldol condensationalone or when coupled with aldol condensation and hydrogenation. Suchcombined processes are highly selective to the corresponding aldehydes.For example, in the case of the terminal olefins, such as alpha-olefinreactants, the following main aldehyde forming reactions take place whenthe present alkyl diaryl phosphine rhodium complex hydroformylation andhydrogenation catalyst is combined with a base catalyst for aldolizationsuch as KOH: ##STR40## wherein the simple n-aldehyde product ofhydroformylation is n-al, the thermally unstable primary product ofaldolization is n,n-hydroxyanol, the unsaturated aldehyde resulting fromdehydration is n,n-enal, and the selectively hydrogenated finalsaturated aldehyde is n,n-anal, wherein the n,n-prefixes indicate thatboth segments of the aldol compounds are derived from the terminal,i.e., normal, product of the hydroformylation. For known, applicablealdolization catalysts, reference is made to Volume 16, Chapter 1 of themonograph Organic Reactions, edited by A. C. Cope et al., published byJ. Wiley and Sons, Inc., New York, N.Y. 1968.

It has been found in accordance with the invention that a combinedhydroformylation/aldolization using alkyl diaryl phosphine ligands, in alarge excess over the rhodium complex catalyst and a high ratio of theH₂ /CO reactant gas resulted in a catalyst system of higher thermalstability and provided a high normal to iso isomer ratio in theproduction of dimer aldehyde product from alpha-olefins. It has beenfound that the presence of a diaryl alkyl phosphine rhodium catalystresults in greater effectiveness for the aldolization step than withbase alone being present. This is especially important for waterinsoluble C₆ and higher aldehyde aldolization with small amounts ofbase, preferably alkali hydroxide.

A combined process also converts some of the i-aldehyde products in aso-called cross-aldolization reaction with the n-aldehyde: ##STR41## Therate of the above cross-aldolization process is slower than that of thesimple aldolization. However, the relative rate of cross-aldolizationincreases with increasing temperature and decreasing n/i aldehyderatios. The latter can be achieved by the addition of extra i-aldehydeto the reaction mixture.

Since high aldolization rates can be readily achieved in a combinedprocess, the reaction parameters can be readily adjusted to provideeither the unsaturated or saturated aldehydes as the major products.Short reaction times, and low olefin conversion, preferably below 50%,plus high base concentration, favor the unsaturated aldehyde. However,mostly the saturated aldol condensation product is desired. This is, ofcourse, the favored high conversion product. It is important to notethat no alcohol by-products are formed even at high olefin conversionsof 80% and higher.

The preferred concentration of the strong inorganic base, i.e., alkalihydroxide, aldolization catalyst is surprisingly low, between about 0.01and 1%, preferably between 0.5 and 0.5%.

Solvent selection is important in a preferred homogeneous, liquid phase,combined process. The preferred solvent will dissolve all the widelydifferent components of the reaction system. Solvency for the nonpolarolefin reactant and polar caustic catalyst and water by-product requirea compromise. Alcohols, particularly hydrocarbyloxyethyl alcohols arepreferred. The latter are preferably of the formula

    J(OCH.sub.2 CH.sub.2).sub.j OH

wherein J=C₁ to C₄ alkyl, preferably primary alkyl, most preferablymethyl; C₆ to C₁₀ substituted or unsubstituted phenyl, preferablyphenyl; and j is an integer of from 1 to 8, preferably from 3 to 8. Suchpreferred solvents include methoxytriglycol, CH₃ (OCH₂ CH₂)₃ OH, andphenoxyethanol, PhOCH₂ CH₂ OH. In general, the weight proportion of therelatively nonpolar hydrocarbyl segment J to that of the highly polaroligo(-oxyethyl) alcohol segment determines the relative solvent powerfor the nonpolar versus polar components of the reaction mixture. Assuch, this type of a solvent can be readily optimized for any specialapplication of the present process. The relatively high overall polarityof this solvent assures both homogeneous reaction and a high n/i ratioof the primary products of the combined process.

With exception of the use of the base and the use of a polar,non-hydrocarbon solvent, the conditions of the present combined processare generally the same as those of a simple hydroformylation.

The following examples are presented for the purpose of illustrating,but not limiting, the present invention.

EXAMPLES Preparation of Alkyl Diaryl Phosphine Ligands

With the exception of the available, simple alkyl diphenyl phosphine andalkylene bis-diphenyl phosphine laboratory chemicals, the ligandcomponents of the present rhodium complexes were prepared during thepresent work.

The generally employed method for ligand preparation was the freeradical chain addition of diphenyl phosphine to a vinylic compound in ananti-Markovnikov manner.

    Ph.sub.2 PH+CH.sub.2 ═CHR→Ph.sub.2 PCH.sub.2 CH.sub.2 R

As a rule, such additions were initiated by broad spectrum ultravioletlight at 15° C. The rate of addition depended strongly on the type ofthe olefinic compound employed. In general, compounds having vinylicsubstitution were highly reactive, while allylic derivatives weresluggish to react. The reaction times were accordingly varied. Theselectivity of the additions could be improved by using more than theequivalent amount, generally 10% excess, of the phosphine adding agent.In the case of vinylic derivatives, this reduced the oligomerization ofthe unsaturated component. With allylic reactants, the phosphine excesssuppressed the allylic reversal reactions of the radical intermediate.

If either the olefinic reactant or adduct product was immiscible with orinsoluble in the diphenyl phosphine adding agent at 15° C., either thetemperature was raised or a solvent was added or both were done toproduce and maintain a homogeneous liquid reaction mixture. During thereaction, the conversion of reactants to products (and by-products) wasfollowed by gas liquid chromatography (glc) and/or proton magneticresonance spectroscopy (pmr). Usually the glc peak intensities were usedto make quantitative estimates of the compositions. For identificationof the product structures nmr was mainly used.

When the desired conversion was reached, the reaction mixture wasusually fractionally distilled in high vacuo to obtain the pure adductproduct. Most of the pure adducts were clear, colorless, mobile liquidsat room temperature. In case of high melting products, recrystallizationof the crude product was used as an alternate means of purification.

The expected structures of the isolated products were confirmed by pmr.Elemental analyses were also performed to check the productcompositions.

The pure phosphines were studied to determine their basicity, directlyby potentiometric titration and indirectly by ³¹ P nmr. The results ofdirect basicity determination will be given below, together with theother analytical characteristics of the free phosphine ligands. The ³¹ Pnmr chemical shift values for the free ligands will be listed ascomparative values when discussing the ³¹ P nmr of their rhodiumcomplexes.

The phosphine basicity determinations via potentiometric titrations wereperformed according to the method of C. A. Streuli. For reference seeAnalytical Chemistry, Vol. 31, pages 1652 to 1654 in 1959 and Vol. 32,pages 985 to 987 in 1960. Half neutralization potentials (HNP's) of thephosphines were determined using perchloric acid as a titrant and purenitromethane, free from weakly basic impurities, as a solvent. Thevalues obtained were subtracted from the HNP of a stronger organic base,diphenyl guanidine, which served as a daily standard reference. Theresulting ΔHNP values of the phosphines are indirectly related to theirbasicity. In case of phosphines which were also studied by Streuli,somewhat different HNP values were obtained in the present work. Sinceion exchange resin purified nitromethane was used in the present work,the reported values should be more correct than Streulis'.

In the following, the preparation of different types of alkyl diarylphosphine ligands will be described in the order of their subsequent usefor forming rhodium complex catalysts. At first the trihydrocarbylsilylsubstituted alkyl diphenyl phosphines will be discussed. They will befollowed by simple alkyl diphenyl phosphines and alkylenebis-phosphines. Finally, the preparation of alkyl diphenyl phosphineshaving different types of substitution will be described. The successfuluse of a variety of ligands then exemplifies the broad scope of theinvention.

Trihydrocarbylsilylethyl Diphenyl Phosphines (Examples 1-6)

Six trihydrocarbylsilylethyl diphenyl silanes were prepared by addingdiphenyl phosphine to the corresponding vinylic or allylic silane. Thepreparation, physical properties and analytical composition of thecompound is summarized in Examples 1-6 below. The table also shows thebasicity characteristics of the products as characterized by their ΔHNPvalues. It is noted that all the trihydrocarbylsilyalkyl diphenylphosphines are much stronger bases than triphenyl phosphine (Ph₃P:ΔHNP=510).

Accounts of the individual experiments are given in the following.

Example 1 Example 1 Preparation of Trimethylsilylethyl DiphenylPhosphine

    Ph.sub.2 PH+CH.sub.2 ═CHSi(CH.sub.3).sub.3 →Ph.sub.2 PCH.sub.2 /CH.sub.2 Si(CH.sub.3).sub.3

A magnetically stirred mixture of 46.5 g (0.25 mole) diphenyl phosphineand 25 g (0.25 mole) of vinyl trimethyl silane in a closed cylindricalquartz tube was irradiated from about 3 cm distance with two 75 WattHanau tube immersion lamps, with a wide spectrum of ultravioletirradiation, in a 15° C. water bath for 26 hours. A proton magneticresonance spectrum of a sample of the resulting mixture exhibited nosignificant peaks in the vinyl region indicating a substantiallycomplete addition.

The reaction mixture was distilled in vacuo to obtain 61 g (81%) of thedesired trimethylsilylethyl diphenyl phosphine adduct, as a clearcolorless liquid, having a boiling range of 109°-110° C. at 0.1 mm.

Anal. Calcd. for C₁₇ H₂₃ PS: C, 71.29; H, 8.09; P, 108.81. Found: C,71.98; H, 8.12; P, 10.59. The ΔHNP (relative half neutralizationpotential compared to that of diphenyl guanidine) was 385.

The selectivity to provide the desired adduct was increased when thediphenyl phosphine reactant was employed in a 10 mole % excess.

Example 2 Preparation of Tripropylsilylethyl Diphenyl Phosphine##STR42##

To prepare the vinyl tripropyl silane reactant, chloro-tri-n-propylsilane was reacted with vinyl magnesium bromide in refluxingtetrahydrofuran. After removing the THF solvent by distillation, theresidual product was taken up in ether, was washed with ice water andthen with 5% aqueous sodium hydrogen carbonate. The ether solution wasthen dried over anhydrous sodium sulfate and distilled to obtain vinyltripropyl silane, bp. 75°-77° C. at 11 mm.

The vinyl tripropyl silane was then reacted with diphenyl phosphine withu.v. initiation for 86 hours in a manner described in Example 1. Theconversion was about 95%. The mixture was fractionally distilled toyield approximately 63% of the theoretical yield of the product as aclear, colorless, mobile liquid. The product distilled at 155°-156° C.at 0.10 mm.

Anal. Calcd. for C₂₃ H₃₅ PSi: C, 74,54; H, 9.52; P, 8.36 Found: C,74.35; H, 923; P, 8.37. The ΔHNP of this compound was 385.

Example 3 Preparation of Triphenylsilylethyl Diphenyl Phosphine##STR43##

To obtain the vinyl triphenyl silane intermediate, vinyl trichlorosilane was reacted with phenyl magnesium bromide in an ether-THF solventmixture. The resulting product was worked up in a manner described inthe previous example. The product was a low melting solid which could bedistilled in vacuo using a hot condenser. At room temperature, thedistillate solidified to yield a white crystalline compound, mp 60°-65°C. Pmr confirmed the expected vinyl triphenyl silane structure.

Anal. Calcd. for C₂₀ H₁₈ Si: C 83.86; H, 6.33. Found: C, 83.92; H, 6.34.The ΔHNP of this compound was 385.

The vinyl triphenyl silane was reacted with 10% excess of diphenylphosphine. To maintain a homogeneous reaction mixture, a temperature of80° C. and cyclohexane solvent ere employed. After the usual u.v.initiated addition, the reaction mixture was allowed to cool to roomtemperature. This resulted in the crystallization of thetriphenylsilyethyl diphenyl phosphine adduct. To obtain it in a pureform, the adduct was filtered and recrystallized from a four to onemixture of cyclohexane and toluene. A white crystalline product having amelting point of 128°-131° C. was obtained.

Anal. Calcd. for C₃₂ H₂₄ Si: C, 81.32; H, 6.19; P, 6.55. Found: C,80.97; H, 6.18; P, 6.71. The ΔHNP of this compound was 413.

Example 4 Preparation of Bis-(Diphenylphosphinoethyl)Dimethyl Silane##STR44##

A mixture of 9.0 g (0.8 mole) dimethyl divinyl silane and 32.7 g (0.176)diphenyl phosphine (10% excess over equivalent amounts) was reacted for22 hours in the manner described in Example 1. The reaction mixture wasfractionated in vacuo to obtain minor amounts of the clear, colorless,slightly viscous liquid monoadduct, and major amounts of the clear,colorless, highly viscous liquid diadduct, i.e. the desiredbis-(diphenylphosphinoethyl)dimethyl silane. The distillation yield ofdesired product was 84%. The bis-diphenylphosphinoethyl)dimethyl silaneproduct had a boiling point of 238°-239° at 0.20 mm.

Anal. Calcd. for C₃₀ H₃₄ P₂ Si: C, 74.35; H, 7.07; P, 12.78. Found: C73.65; H, 6.90; P, 12.59. The ΔHNP of this compound was 434.

Example 5 Preparation of Trimethylsilylpropyl Diphenyl Phosphine

    Ph.sub.2 PH+CH.sub.2 ═CHCH.sub.2 Si(CH.sub.3).sub.3 →Ph.sub.2 PCH.sub.2 Ch.sub.2 CH.sub.2 Si(CH.sub.3).sub.3

A mixture of 22.8 g (0.2 mole) allyl trimethyl silane and 37.2 g (0.2mole) diphenyl phosphine was reacted for 158 hours in the mannerdescribed in Example 1. A subsequent fractional distillation, yieldedthe desired pure adduct as a clear, colorless liquid. The distillationyield was 50%. The product had a boiling point of 150° C. at 0.10 mm.

Anal. Calcd. for C₁₈ H₂₅ PSi: C, 71.96; H, 8.38; P, 10.31. Found: C,72.27; H, 8.29; P, 10.25. The ΔHNP for this product was 408.

Example 6 Preparation of Trimethylsilylmethyl Diphenyl Phosphine

    Ph.sub.2 PLi+ClCH.sub.2 Si(CH.sub.3).sub.3 →Ph.sub.2 PCH.sub.2 Si(CH.sub.3).sub.3

The known but unavailable trimethylsilylmethyl diphenyl phosphine wasderived via reacting chloromethyl trimethyl silane with lithium diphenylphosphide in an ether-hexane mixture. After removing the lithiumchloride by-product by filtration, the product was isolated as a clear,colorless liquid by fractional distillation in vacuo. The distillationyield ws 86% and the product had a boiling point of 129°-130° C. at 0.2mm.

Anal. Calcd. for C₁₆ H₂₁ PSi: C, 70.55; H, 7.77; P, 11.37. Found: C,70.01; H, 7.64; P, 11.36. the ΔHNP for the product was found to be 404.

Alkyl Diaryl Phosphines (Examples 7-15)

For a study of the influence of the alkyl structure in alkyl diphenylphosphine ligands, a number of commercially available compounds wereobtained (Table 1, Example Nos. 7 to 11). The known but unavailableneopentyl diphenyl phosphine and 3,3-dimethylbutyl diphenyl phosphine(Table 1, Example Nos. 12 and 13, respectively) were synthesized byreacting the corresponding alkyl chlorides with lithium diphenylphosphide.

Table 2 lists the relative half neutralization potentials of the variousalkyl diphenyl phosphines. It is noted that as a group they are muchmore basic than triphenyl phosphine. The branching of the alkyl group,particularly in the proximity of the phosphorus, further increases thebasicity.

                  TABLE 1                                                         ______________________________________                                        Alkyl Diphenyl Phosphine Ligands and Their Basicity                                                        Indirect                                         Example                      Basicity                                         No.       Structure          Δ HNP                                      ______________________________________                                         7.sup.a  Ph.sub.2 PCH.sub.2 CH.sub.3                                                                      363                                               8.sup.b  Ph.sub.2 PCH.sub.2 CH.sub.2 CH.sub.3                                                             424                                               9.sup.a  Ph.sub.2 PCH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                    404                                              10.sup.b  Ph.sub.2 PCH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                  392                                              11.sup.b                                                                                 ##STR45##         355                                              12.sup.a  Ph.sub.2 PC(CH.sub.3).sub.3                                                                      341                                              13.sup.c  Ph.sub.2 PCH.sub.2 C(CH.sub.3).sub.3                                                             378                                              14.sup.c  Ph.sub.2 PCH.sub.2 CH.sub.2 C(CH.sub.3).sub.3                                                    412                                              15.sup.a                                                                                 ##STR46##         372                                              Standard  Ph.sub.3 P         510                                              ______________________________________                                         .sup.a Purchased from Strem Chemicals Inc., Newburyport, Mass.                .sup.b Purchased from Organometallics Inc., East Hampstead, N.H.              .sup.c Prepared by reacting lithium diphenyl phosphide with the               corresponding alkyl chloride.                                            

Example 13 Preparation of Neopentyl Dimethyl Phosphine

    Ph.sub.2 PLi+ClCH.sub.2 C(CH.sub.3).sub.3 →Ph.sub.2 PCH.sub.2 C(CH.sub.3).sub.3

The known but unavailable 2,2-dimethylpropyl diphenyl phosphine wasderived via reacting 2,2-dimethylpropyl chloride with lithium diphenylphosphide in a refluxing tetrahydrofuran-hexane solvent mixture. Afterfiltering off the lithium chloride by-product, the 2,2-dimethylpropyl,(i.e., neopentyl)diphenyl phosphine was obtained by the fractionaldistillation of the filtrate between 109° and 110° C. at 0.1 mm.

Example 14 Preparation of 3,3-Dimethylbutyl Diphenyl Phosphine

    Ph.sub.2 PH+CH.sub.2 ═CHC(CH.sub.3).sub.3 →Ph.sub.2 PCH.sub.2 CH.sub.2 C(CH.sub.3).sub.3

Diphenyl phosphine and t-butylethylene, i.e. 3,3-dimethyl butene, werereacted in the manner of Example 1. However, some phase separationoccurred, and consequently, the reaction was slow. The expected adductwas separated from the reactants by fractional distillation. It wasobtained as a colorless, clear liquid, boiling between 125°-127° C. at0.2 mm.

As a known compound, t-butylethyl, (i.e., 3,3-dimethylbutyl)diphenylphosphine was also synthesized via the known displacement approach: thereaction of lithium diphenyl phosphide with 3,3-dimethylbutyl chlorideprovided the compound in good yield.

Alkylene Bis-(Diphenyl Phosphines) (Examples 16-22)

As a class of compounds alkylene bis-diphenyl phosphines are known. Inthe present work, available compounds were used. The bis-phosphines assuch were studied only to determine their basicity. The results areshown in Table 2. According to the results at the transition fromchelating to non-chelating phosphines (n=3 to n=4) different phosphinespecies are present as indicated by the pairs of ΔHNP values.

                  TABLE 2                                                         ______________________________________                                        Alkylene Bis-(Diphenyl Phosphine) Ligands and Their Basicity                  Ph.sub.2 P(CH.sub.2).sub.m PPh.sub.2                                                                   Indirect                                                          Polymethylene                                                                             Basicity                                             Example      Bridge, m   ΔHNP                                           ______________________________________                                        16           1           453                                                  17           2           431                                                  18           3           395, 548 .sup.                                       19           4           315, 378 .sup.                                       20           5           --                                                   21           6           423                                                  22           14          --                                                   ______________________________________                                    

Variously Substituted Alkyl Diphenyl Phosphines (Examples 23-47)

All the ligands which will be subsequently described were prepared bythe addition of diphenyl phosphine to differently substituted vinyliccompounds. Most of the adducts are novel, and none of them werepreviously prepared by the present method.

Example 23 Preparation of Phenylethyl Diphenyl Phosphine

    Ph.sub.2 PH+CH.sub.2 ═CHPh→Ph.sub.2 PCH.sub.2 CH.sub.2 Ph

2-Phenylethyl diphenyl phosphine, a known but unavailable compound, wasprepared in the present work via a new method, i.e., the addition ofdiphenyl phosphine to styrene. A mixture of the unsaturated compound(20.8 g, 0.20 mole) and the phosphine (39.1 g, 0.21 mole, 5% excess) wasirradiated for 5 hours in the usual manner. The desired adduct,2-phenylethyl diphenyl phosphine, was obtained as a pure colorless,clear liquid distillate by distillation in vacuo. The distillation yieldwas 87% and the product had a boiling point of 171°-173° C. at 1 mm.(Table 3).

Example 24 Preparation of Pyrrolidinonylethyl Diphenyl Phosphine##STR47##

A mixture of 37.2 (0.2 mole) diphenyl phosphine and 22.2 g (0.2 mole)N-vinyl-2-pyrrolidinone was reacted with U.V. initiation for 48 hours.GLC analyses of the reation mixture indicated that after 5, 24 and 48hours the conversions to the desired adduct were 63, 93 and 99%respectively. The crude product was purified by distillation to obtainpure N-2-pyrrolidinonylethyl diphenyl phosphine as a hazy, colorless,viscous liquid (Table 3).

                                      TABLE 3                                     __________________________________________________________________________    Preparation, Physical Properties and Composition of Various Substituted       Alkyl Diphenyl Phosphine Ligands                                              __________________________________________________________________________                                            Ligand Distd                          Example                                                                            Example                            Bp. °C./mm                                                                    Yield                          No.  No. E-                                                                              Structure of Ligand                                                                          Unsaturated Reactant Used                                                                   (Mp. °C.)                                                                     ˜%                       __________________________________________________________________________    23   4275-VI                                                                             Ph.sub.2 PCH.sub.2 CH.sub.2 Ph                                                               CH.sub.2CHPh  171-173/0.1                                                                          87                             24   5382-IX                                                                              ##STR48##                                                                                    ##STR49##    181-178/0.1                                                                          83                             25   5433-IX                                                                             Ph.sub.2 PCH.sub.2 CH.sub.2 CH.sub.2 N(C.sub.2 H.sub.5).sub.2                                CH.sub.2CHCHN(C.sub.2 H.sub.5).sub.2                                                        137-138/0.1                                                                          --                             26   5431-VIII                                                                           Ph.sub.2 PCH.sub.2 CH.sub.2 SO.sub.2 C.sub.2 H.sub.5                                         CH.sub.2CHSO.sub.2 C.sub.2 H.sub.5                                                          .sup.b 69                             27   5421-III                                                                            Ph.sub.2 PCH.sub.2 CH.sub.2 POPh.sub.2                                                       CH.sub.2CHPOPh.sub.2                                                                        (182-184.sup.a)                                                                       41.sup.a                      28   5391-XII                                                                            Ph.sub.2 PCH.sub.2 CH.sub.2 COCH.sub.3                                                       CH.sub.2CHCOCH.sub.3                                                                        148-150/                                                                             56                                                                     0.09-0.08                             29   5384-X                                                                              Ph.sub.2 PCH.sub.2 CH.sub.2 CO.sub.2 CH.sub.3                                                CH.sub.2CHCO.sub.2 CH.sub.3                                                                 162-160/                                                                             60                                                                     0.30-0.32                             __________________________________________________________________________                                Elemental Composition                                                                           Inverse                                          Example                                                                            Example                                                                             Calcd.   Found    Basicity                                         No.  No. E-                                                                              C  H  P  C  H  P  Δ HNP                     __________________________________________________________________________                     23   4275-VI                                                                             82.74                                                                            6.60                                                                             10.66                                                                            82.30                                                                            6.67                                                                             10.77                                                                            416                                              24   5382-IX                                                                             72.71                                                                            6.89                                                                             10.42                                                                            72.31                                                                            6.71                                                                             10.50                                                                            450                                              25   5433-IX                                                                             76.22                                                                            8.75                                                                              4.68                                                                            76.55                                                                            8.76                                                   26   5431-VIII                                                                           62.73                                                                            6.25                                                                             10.11                                                                            62.49                                                                            6.17  543                                              27   5421-III                                                                            75.36                                                                            5.84                                                                             14.99                                                                            74.85                                                                            5.84                                                                             14.52                                                                            430                                              28   5391-XII                                                                            74.99                                                                            6.69                                                                             12.08                                                                            74.53                                                                            6.58                                                                             11.82                                                                            425                                              29   5384-X                                                                              70.58                                                                            6.29                                                                             11.38                                                                            70.81                                                                            6.31                                                                             11.25                                                                            455                             __________________________________________________________________________     .sup.a Recrystallized from methanol                                           .sup.b Recrystallized from 1propanol which was also used as the solvent       for the reaction.                                                        

Example 25 Preparation of Diethylaminopropyl Diphenyl Phosphine

    Ph.sub.2 PH+CH.sub.2 ═CHCH.sub.2 N(C.sub.2 H.sub.5).sub.2 →Ph.sub.2 PCH.sub.2 CH.sub.2 CH.sub.2 N(C.sub.2 H.sub.5).sub.2

A mixture of 17 g (0.15 mole) allyl diethyl amine and 30.7 g (0.165mole, 10% excess) of diphenyl phosphine is reacted in the usual mannerwith u.v. irradiation for 17 hours. A subsequent analysis of thereaction mixture indicated that about one third of the reactants wasconverted. The only product formed was the desired adduct,2-diethylaminopropyl diphenylphosphine. It was isolated as a clearcolorless liquid (Table 3).

Example 26 Preparation of Ethylsulfonylethyl Diphenyl Phosphine

    Ph.sub.2 PH+CH.sub.2 ═CHSO.sub.2 C.sub.2 H.sub.5 →Ph.sub.2 PCH.sub.2 CH.sub.2 SO.sub.2 C.sub.2 H.sub.5

A mixture of 64 g (0.34 mole) of diphenyl phosphine and 40.2 g (0.33mole) of highly reactive, freshly distilled vinyl ethyl sulfone monomerwas irradiated in the usual manner. To suppress polymer forming sidereactions the temperature of the reaction mixture was kept below 5° C.by an ice-water bath and the u.v. irradiation was limited to 105minutes. The adduct formed crystallized from the liquid mixture by theend of the reaction period. Consequently, the reaction mixture wasfiltered with suction to recover the crude, crystalline product, i.e.2-ethylsulfonylethyl diphenyl phosphine. The crude, dried product (94 g,94) was recrystallized from 670 ml methanol to yield 69 g (69%) of thecompound (of unpleasant odor) as a white crystalline solid (Table 3).

Example 27 Preparation of Diphenylphosphinoethyl Diphenyl PhosphineOxide ##STR50##

2-Diphenylphosphinoethyl diphenyl phosphine oxide, a known, butunavailable compound, was prepared via a new approach. In the firststep, diphenyl phosphine was quantitatively air oxidized at 60° C. inisopropanol solution. The resulting diphenyl phosphine oxide was thenadded to vinyl diphenyl oxide in the manner of Example 1, with u.v.initiation.

A 26.5 wt% by wt isopropanol solution of 33.9 g (0.16 mole) of thephosphine oxide adding agent and 34.1 g (0.16 mole) of the vinylphosphine reagent were mixed. The resulting homogeneous liquid mixturewas irradiated with stirring at 30° C. for 66 hours. By the end of thereaction period, the adduct formed crystallized from the mixture.Subsequently, the crude product was dissolved in refluxing isopropanolafter adding an additional 124 g of the solvent. A glc analysis of thehot solution showed that the desired addition was complete and no sidereaction occurred. Consequently, the solution was allowed to cool. Thisresulted in the crystallization of the product. The latter was separatedby filtration with suction and washing with cold isopropanol. Subsequentdrying in vacuo provided 66 g (41%) of the pure compound as a whitecrystalline solid (Table 3).

Example 28 Preparation of Acetylethyl Diphenyl Phosphine ##STR51##

To 37.2 g (0.2 mole) stirred, nitrogen blanketed diphenyl phosphine,15.2 g (0.22 mole) of the highly reactive vinyl ethyl ketone reactantwas added dropwise. During the addition an exothermic reaction tookplace. As a consequence, the temperature of the reaction mixture rose to50° C. A subsequent GLC analysis indicated that the vinyl reactant wasmostly converted. Major amounts of the desired adduct and minor amountsof the diadduct were formed. The adduct, i.e. 2-acetylethyl diphenylphosphine, was obtained by fractional distillation of the reactionmixture. At room temperature, it solidified to a light yellow substance(Table 3).

Example 29 Preparation of Carbomethoxyethyl Diphenyl Phosphine ##STR52##

A mixture of 8.6 g (0.1 mole) methyl acrylate and 19.5 g (0.105 mole, 5%excess) of diphenyl phosphine was reacted at 15° C. in the routinemanner of Example 1. U.V. irradiation resulted in a rapid reaction.After 1 hour, there was no acrylate left unconverted. The expected mono-and diadducts were formed in a weight ratio of about 95° to 5. (A sampleof the reaction misture which was not irradiated also showed a completeconversion after 22 hours but not after 1 hour.) On distillation of thereaction mixture in vacuo, the monoadduct, i.e. 2-carbomethoxyethyldiphenyl phosphine, was obtained as an almost colorless, liquiddistillate having a slight yellow tint (Table 3).

Example 30 Preparation of Hydroxypropyl Diphenyl Phosphine

    Ph.sub.2 PH+CH.sub.2 ═CHCH.sub.2 OH→Ph.sub.2 PCH.sub.2 CH.sub.2 CH.sub.2 OH

A mixture of 11.5 g (0.062 mole) diphenyl phosphine and 3.6 g (0.062mole) of allyl alcohol was reacted with irradiation initiation at 15° C.for 110 hours in the usual manner. Subsequent glc and nmr analysesindicated complete conversion to the desired adduct, i.e.3-hydroxypropyl diphenyl phosphine. Distillation in vacuo provided 10.5g (72%) of the pure compound, between 162°-164° C. at 0.15 mm, as aclear colorless liquid.

Anal. Calcd. for C₁₅ H₁₇ OP: C, 73.76; H, 7.01; P, 12.68. Found: C,73.52; H, 6.89; P, 12.82.

Example 31 Preparation of Bis-(Diphenylphosphinopropyl) Ether

    2Ph.sub.2 PH+(CH.sub.2 ═CHCH.sub.2).sub.2 O→(Ph.sub.2 PCH.sub.2 CH.sub.2 CH.sub.2).sub.2 O

A mixture of 7.3 g (0.75 mole) diallyl ether and 30.7 g (0.165 mole, 10%excess over the mole equivalent amount) was irradiated at 15° C. for 3days to effect the desired addition. Glc showed that the conversion ofdiphenyl phosphine was about 66%. The major product, about 50% of themixture was the desired diadduct, bis-(3-diphenylphosphinopropyl) ether.The pure diadduct was obtained by distillation in vacuo.

Example 32 Preparation of Methylthiopropyl Diphenyl Phosphine

    Ph.sub.2 PH+CH.sub.2 ═CHCH.sub.2 SCH.sub.3 →Ph.sub.2 PCH.sub.2 CH.sub.2 CH.sub.2 SCH.sub.3

A mixture of 10.6 g (0.12 mole) of allyl methyl ether and 24.6 g (0.132mole, 10% excess) diphenyl phosphine was reacted at 15° C. with u.v.initiation for 28 hours. Glc indicated an essentially complete butnonselective conversion of the reactants. The selectivity to the desiredadduct, 3-methylthiopropyl diphenyl phosphine, was about 50%. Ondistillation in vacuo 13 g (40%) of the compound was obtained as aclear, colorless liquid, bp. 150°-152° C. at 0.2 mm.

Anal. Calcd. for C₁₄ H₁₉ PS: C, 70.04; H, 6.98; P, 11.29; S, 11.69.Found: C, 69.78; H, 6.82; P, 11.35; S, 11.93.

Examples 33-47 Miscellaneous Substituted Alkyl Diaryl Phosphines

Using the methods described in the previous examples, diphenyl phosphinecan be added to a number of vinylic and allylic compounds to yield thecorresponding anti-Markovnikov adducts, i.e. substituted alkyl diphenylphosphines, as shown by the following tabulation.

    ______________________________________                                                Unsaturated                                                                   Reagent                                                               Example for Diphenyl Substituted Alkyl                                        No.     Phosphine    Diphenyl Phosphine                                       ______________________________________                                        33      Vinyl naphthalene                                                                          Naphthyl ethyl diphenyl                                                       phosphine                                                34      Allyl amine  Aminopropyl diphenyl                                                          phosphine                                                35      Allyl morpholine                                                                           Morpholinopropyl diphenyl                                                     phosphine                                                36      Acrylamide   Carbamylethyl diphenyl                                                        phosphine                                                37      Vinyl carbazole                                                                            Carbazylethyl diphenyl                                                        phosphine                                                38      Vinyl pyridine                                                                             Pyridylethyl diphenyl                                                         phosphine                                                39      Vinyl phthalimide                                                                          Phthalimidoethyl diphenyl                                                     phosphine                                                40      Vinyl diethyl                                                                              Diethyoxyphosphonylethyl                                         phosphonate  diphenyl phosphine                                       41      Allyl ethyl ether                                                                          Ethoxypropyl diphenyl                                                         phosphine                                                42      Vinyl isopropyl                                                                            i-Propoxyethyl diphenyl                                          ether        phosphine                                                43      Vinyl furan  Furylethyl diphenyl phosphine                            44      Allyl acetate                                                                              Acetoxypropyl diphenyl                                                        phosphine                                                45      Vinyl benzoate                                                                             Benzoyloxyethyl diphenyl                                                      phosphine                                                46      Allyl phenyl Phenylthiopropyl diphenyl                                        sulfide      phosphine                                                47      Divinyl sulfone                                                                            Bis-(diphenylphosphinoethyl)                                                  sulfone                                                  ______________________________________                                    

Similar additions are carried out using di-4-tolyl phosphine anddifluorophenyl phosphine and the above unsaturated reactants to yieldthe corresponding ring substituted products.

Preparation and Properties of Tris-(Alkyl Diaryl Phosphine) RhodiumCarbonyl Hydride Complexes Preparation from Rhodium Chloride Example 48Preparation of Tris-(Trimethylsilylethyl Diphenyl Phosphine) RhodiumCarbonyl Hydride

    3(Ph.sub.2 PCH.sub.2 CH.sub.2 Si(CH.sub.3).sub.3 +RhCl.sub.3.3H.sub.2 O→[Ph.sub.2 PCH.sub.2 CH.sub.2 Si(CH.sub.3).sub.3 ].sub.3 Rh(CO)H

To a vigorously stirred, refluxing, nitrogenated solution of 11.44 g (40mmole) of (trimethylsilylethyl) diphenyl phosphine of Example 1 in 400ml of ethanol, a hot solution of 1.04 g (0.4 mmole) of rhodiumtrichloride trihydrate in 80 ml ethanol was added at once. After a delayof 15 seconds, 40 ml warm aqueous (37%) formaldehyde solution and,immediately thereafter, 80 ml hot ethanolic solution of 3.2 g ofpotassium hydroxide were added. The resulting clear orange liquidreaction mixture was refluxed for 10 minutes. During the heating, thecolor changed to deep orange.

The mixture was cooled to -25° C. to crystallize the complex product.Crystallization started at -10° C. and was completed on standing forabout 2 hours at -25° C. The crystalline complex was separated byfiltration through a precooled Buechner funnel with suction and washingsuccessively with 20 ml cold portions of ethanol, water, ethanol andn-hexane. The complex was then dried in the presence of anhydrouscalcium chloride at 9.1 mm over the weekend. As a result, 2.2 g (2.2mmole, 55%) of dry tris-(trimethylsilylethyl diphenyl phosphine) rhodiumcarbonyl hydride complex was obtained as a fine crystallineorange-yellow powder. In a sealed capillary tube, the complex meltedbetween 126°-129° C. to a clear dark red liquid. In an open capillary,complete melting occurred at 121° C. There was no sign of decompositionon heating up to 140° in either case.

The infrared spectrum of the complex in Nujol showed a strong carbonylband of 1985 cm⁻¹ and a band of medium intensity at 1900 cm⁻¹.

Analyses Calcd. for C₅₂ H₇₀ OP₃ RhS: C, 63.01; H, 7.12; P, 9.38; Found:C, 62.89; H, 7.06; P, 9.59.

Preparation from Tris-(Triphenyl Phosphine) Rhodium Carbonyl Hydride ViaLigand Displacement

    (PH.sub.3 P).sub.3 Rh(CO)H+3Ph.sub.2 PR→(Ph.sub.2 PR).sub.3 Rh(CO)H+3Ph.sub.3 P

The tris-(alkyl diaryl phosphine) rhodium carbonyl hydride complexeswere prepared be reacting the readily available tris-(triphenylphosphine) rhodium carbonyl hydride (from Engelhard Minerals andChemicals Corporation, Newark, N.J.) with the corresponding alkyl diarylphosphines. Generally, the reactions were performed in a mixture oftoluene and deuterated benzene as a solvent under a nitrogen blanket.The deuterated benzene component was used as a primary nmr standard.

At first, a solution of about 5% of the alkyl diaryl phosphine reactantwas prepared. To samples of the solution, TPP rhodium carbonyl hydridewas added in equivalent and half equivalent amounts. The resultingmixtures were magnetically stirred until homogeneous liquids wereobtained. Additional amounts of the toluene solvent were used if needed.The homogeneous reaction mixture was then studied by ³¹ P nmrspectroscopy. Chemical shifts were measured by assigning a shift of OPPM to the frequency at which 1M H₃ PO₄ would resonate.

The ³¹ P nmr experiments were carried out using a JEOL FX 900multi-nuclear nmr spectrometer. When required the experimentalconditions were adjusted, i.e. the ¹ H-³¹ P decoupling was removed andlonger delays between pulses were employed, to determine the relativepopulations of free and rhodium bound alkyl diphenyl phosphine and TPP.

The ³¹ P nmr experiments are illustrated in FIG. 2 which shows thespectrum of a six to one mixture of n-butyl diphenyl phosphine andtris-TPP rhodium carbonyl hydride, in comparison with a spectrum of athree to one mixture of TPP and tris-TPP rhodium carbonyl hydride.

In the presence of excess butyl diphenylphosphine, the only significantdoublet peak of complexed phosphorus is that derived from butyl diphenylphosphine. This complex was derived by ligand exchange as indicated bythe singlet of displaced free TPP. Although the doublet of the butyldiphenyl phosphine complex has a chemical shift value different fromthat of TPP, the coupling constants are about the same for bothcomplexes. The coupling constant and chemical shift difference betweenbound and free ligand indicate that both ligands form tris-(phosphine)rhodium carbonyl hydrides.

Similar ligand exchange experiments were carried out with other alkyldiphenyl phosphines to form their tris-(phosphine) rhodium carbonylhydride complexes to determine the characteristic nmr parameters of suchcomplexes.

The nmr parameters of the trihydrocarbylsilylalkyl diphenyl phosphinecomplexes are shown by Table 4. The most characteristic parameter is thechemical shift value of the rhodium complexed ligand. For comparison,the chemical shift values of the free ligands are also tabulated.Complexation of rhodium of the phosphine apparently produced a similardownfield charge of the shift values. Finaly, it is also noted inreference to the table, that even the limited exposure of the rhodiumcomplexed phosphines to air resulted in some oxidation to thecorresponding phosphine oxides. The latter exhibited sharp singletsslightly upfield from the complexed phosphine.

The data of Table 4 shows that with the exception of the last compoundall the phosphines ligands form similar well characterizable complexesat room temperature. The line shapes of the signals showed little butvarying broadening, i.e., ligand exchange. In the case of thetris-(trimethylsilylethyl diphenyl phosphine), tris-SEP, rhodiumcarbonyl hydride complex (Example 48), there was moderately slow ligandexchange between free and complexed phosphines. The exchange mechanismis illustrated for the SEP complex by the following (for details of thehydroformylation mechanism refer to FIG. 1): ##STR53##

The line shapes of signals for the SEP complex and the known TPP complexare compared by FIG. 3 at various temperatures. At first, the 30° C.spectra will be discussed. These spectra indicate that at 30° C., thereis a similar, ligand exchange rate between the new SEP and the known TPPcomplex.

                                      TABLE 4                                     __________________________________________________________________________    .sup.3 P NUCLEAR MAGNETIC RESONANCE PARAMETER OF FREE AND                     RHODIUM-COMPLEXED                                                             TRIHYDROCARBYLSILYLALKYL DIPHENYL PHOSPHINES                                                                                      Chemical                                                          Coupling                                                                            Chemical                                                                            Shift                                                   Chemical Shift                                                                          Constant                                                                            Shift Difference                Example                                                                            Example                  σ, ppm                                                                            .sup.J P-Rh                                                                         σ, ppm                                                                        Δσ, ppm       No. of                                                                             No. of                                                                             Chemical Structure  Free                                                                              Complexed                                                                           Complexed                                                                           Phosphine                                                                           Complex                   Complex                                                                            Ligand                                                                             of Complex          Ligand                                                                            Ligand                                                                              Ligand                                                                              Oxide Ligand                    __________________________________________________________________________    --   --   (Ph.sub.3 P).sub.3 [Rh(CO)H] Reference)                                                            -7.5                                                                             +38.3 155         45.8                      48   1    [Ph.sub.2 PCH.sub.2 CH.sub.2 Si(CH.sub.3).sub.3 ].sub.3                       [Rh(CO)H]           -12.1                                                                             +34.6 150   +27.0 46.9                      49   2    [Ph.sub.2 PCH.sub.2 CH.sub.2 Si(C.sub.3 H.sub.7).sub.3 ].sub.3                [Rh(COH]            -11.2                                                                             +34.8 151   +29.9 45.0                      50   3    (Ph.sub.2 PCH.sub.2 CH.sub.2 SiPh.sub.3).sub.3 [Rh(CO)H]                                          -10.6                                                                             + 35.5                                                                              151   +21.1 46.1                      51   4    [(Ph.sub.2 PCH.sub.2 CH.sub.2).sub.2 Si(CH.sub.3).sub.2 ].sub.3               [Rh(CO)H]           -12.2                                           52   5    [Ph.sub.2 PCH.sub.2 CH.sub.2 CH.sub.2 Si(CH.sub.2).sub.3                      ].sub.3 [Rh(CO)H]   -19.7                                                                             +26.6 154   +24.6 46.3                      53   6    [Ph.sub.2 PCH.sub.2 Si(CH.sub.3).sub.3 ].sub.3 [Rh(CO)H]                                          -24.4                                                                             +17.0 .sup. 133.sup.a                                                                     +23.9 41.4                      __________________________________________________________________________     .sup.a The .sup.31 P  .sup.103 Rh coupling was not resolved at room           temperature but was clearly resolved at 60° C.                    

The tris-SEP complex and two other trimethylsilylalkyl diphenylphosphine complexes (Examples 51 and 52) showed a very similar ligandexchange behavior at 30° C. The tripropylsilylethyl diphenyl phosphinecomplex (Example 49) exhibited a definitely slower exchange rate. Theexchange rate of the triphenylsilylethyl diphenyl phosphine complex(Example 50) was even much slower than that. It appeared thatsubstituted alkyl diphenyl phosphine ligands of increasing bulkiness haddecreasing ligand exchange rates. In both cases though, the TPP ligandexchanged less rapidly than the alkyl diphenyl phosphine.

Finally, it is noted that when even a moderately bulky alkyl substituentwas close to the phosphorus, i.e., in the case of trimethylsilymethyldiphenyl phosphine, the complexation of phosphorus to the rhodium wasinhibited (Example 54). In that case, there was no distinct complexformation with the sterically hindered ligand at 30° C. At -60° C., astable complex was formed. However, this complex was decomposed when itssolution was heated under hydroformylation process conditions.

As far as ligand exchange rates at higher temperatures are concerned,the results shown by FIG. 3 are typical. FIG. 3 shows the comparison oftwo systems: tris-triphenyl phosphine rhodium carbonyl hydride plustriphenyl phosphine and tris-trimethylsilylethyl diphenyl phosphinerhodium carbonyl hydride plus triphenyl phosphine. The latter system isthe result of equilibrating the TPP complex with trimethylsilylethyldiphenyl phosphine (SEP):

    (Ph.sub.3 P).sub.3 Rh(CO)H+3Ph.sub.2 PCH.sub.2 CH.sub.2 SiMe.sub.3 →[Ph.sub.2 PCH.sub.2 CH.sub.2 SiMe.sub.3 ].sub.3 Rh(CO)H+3Ph.sub.3 P

SEP being a substituted alkyl diphenyl phosphine, was found to be astronger complexing agent that TPP. The spectra of both systems weretaken under comparative conditions at 30°, 60° and 90°.

The line shapes of the signals of the 30° C. showed little signalbroadening in both cases. This indicated comparably slow exchange ratesof about 25 per second. In alternative terms, relatively long averageexchange lifetimes, in the order of 2×10⁻² sec, were indicated for bothtris-phosphine complexes. At 60°, considerable line broadening occurred,indicating a much faster exchange. The exchange acceleration was greaterin the case of the TPP system (k=600 vs. 80). The average lifetime wasabout 3×10⁻³ sec for the TPP system and 6×10⁻³ sec for the SEP system.At 90°, only a single, borad signal could be observed for the TPP systemwhile the SEP system still exhibited separate, although extremely broad,chemical shift ranges for the complexed and free phosphorus species.Apparently, the exchange acceleration in the case of the TPP system wastremendous. The average lifetime between exchanges was reduced about twoorders of magnitude to 5×10⁻⁵ sec (k≈10,000). In the case of the SEPsystem, the average lifetime dropped by about one order to 5×10⁻⁴ sec(k≈1,500). It must be emphasized that the exchange rates and lifetimesreported here may change somewhat when the lineshape is subjected to arigorous computer analysis. The relative order of their values willremain unaltered, however.

It is interesting to note that there was no great change of equilibriawith the increasing exchange rates. Apparently, both ligand eliminationand addition increase similarly in this temperature range. Thetris-phosphine rhodium species remained the dominant form of complexes.In the SEP complex plus free TPP system, the rhodium remainedpredominantly complexed to the SEP.

The role of excess phosphine ligand is apparently to maintain theequilibria in favor of the tris-phosphine complex, i.e. to reduce boththe concentration and average lifetime of the unstable and highlyreactive bis-phosphine complex. The increased ligand exchange rateprovides enough active bis-phosphine complex catalytic species for fasthydroformylation, without leading to noncatalytic side reactions, i.e.catalyst decomposition.

In summary, the above and similar ligand exchange rate studies indicatethat, in the presence of excess ligand, the alkyl diaryl phosphinerhodium complexes are catalytically activated at higher temperaturesthan the known triaryl phosphine rhodium complexes.

The results of a similar systematic ³¹ P study of various alkyl diphenylphosphines is summarized in Table 5. The Table shows the ³¹ P nmrparameters of free and rhodium complexed alkyl diphenyl phosphines insolution at 35°. An overview of Table 5 indicates that five of the sevenphosphine ligands examined formed tris-phosphine rhodium carbonylhydride complexes. Steric crowding apparently inhibited complexformation. Comments on the detailed data of the table are made in thefollowing.

As it was already discussed in conjunction with FIG. 2, n-butyl diphenylphosphine exhibits a ligand exchange behavior similar to that of the SEPligand (Example 54). However, it was slightly less effective incompletely displacing TPP. In the latter respect, the bulkier n-hexyldiphenyl phosphine was a more effective ligand (Example 55).

In comparison to n-butyl diphenyl phosphine, secondary butyl diphenylphosphine is quite ineffective in replacing the TPP ligand (Example 56).Cooling to -60° was necessary to observe a clearly resolved doubletsignal for the complexed secondary butyl compound. Alternatively, acomplex of this ligand could be obtained at room temperature startingwith (PH₃ As)₃ Rh(CO)H (TPA complex) in place of the TPP complex.

                                      TABLE 5                                     __________________________________________________________________________    .sup.31 P NUCLEAR MAGNETIC RESONANCE PARAMETER OF FREE AND                    RHODIUM COMPLEXED ALKYL DIPHENYL PHOSPHINES                                                                           Coupling                                                                            Chemical Shift                                                Chemical Shift                                                                          Constant                                                                            Difference                      Example                                                                            Example                  σ, ppm                                                                            J.sub.P--Ph                                                                         Δσ, ppm             No. of                                                                             No. of                                                                             Chemical Structure  Free                                                                              Complexed                                                                           Complexed                                                                           Complex                         Complex                                                                            Ligand                                                                             of Complex          Ligand                                                                            Ligand                                                                              Ligand                                                                              Ligand                          __________________________________________________________________________    54    9   (φ.sub.2 PCH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3).sub.3                      Rh(CO)H             -18.6                                                                             +27.4 149.sup.                                                                            46.0                            55   10   (φ.sub.2 PCH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2                    CH.sub.3).sub.3 Rh(CO)H                                             56   11                                                                                  ##STR54##           -4.8                                                                             +40.0 154.sup.a                                                                           45.0                            57   12   (φ.sub.2 PC(CH.sub.3).sub.3 ].sub.3 Rh(CO)H                                                   -25.1                                           59   14   [φ.sub.2 PCH.sub.2 CH.sub.2 C(CH.sub.3).sub.3 ].sub.3                     Rh(CO)H             -16.8                                                                             +27.5 152.sup.                                                                            44.3                            60   15                                                                                  ##STR55##           -5.9                                                                             +42.0 152.sup.a                                                                           -48                             __________________________________________________________________________     .sup.a The .sup.31 P-- .sup.103 Rh coupling was not resolved at room          temperature but was clearly resolved at 60° C.                    

Tertiary butyl and neopentyl diphenyl phosphine (Examples 57 and 58) didnot form tris-phosphine complexes under standard experimentalconditions. Surprisingly, the t-butyl compound had a destabilizingeffect on the TPP complex reactant. As a result the mixture rapidlyturned black, apparently due to rhodium precipitation.

3,3-Dimethylbutyl diphenyl phosphine exhibited a complex forming andequilibriation tendencies similar to those of its silicon analog, SEP.

Finally, it is noted that cyclohexyl diphenyl phosphine only partiallyreplaced TPP from its complex and exhibited a very high rate of ligandexchange (Example 60). Overall this ligand and the secondary butyldiphenyl phosphine had a comparable complexing behavior. In both cases,steric crowding was a severely limiting factor.

The third type of ligands studied by ³¹ P nmr in a similar manner werealkylene bis-(diphenyl phosphines). The parameters obtained for the freeand complexed ligands of this type are summarized in Table 6. The firstthree bis-phosphines of the table are chelate forming compounds(Examples 61-63). These were studied for comparison only. The next fourcompounds, i.e. polymethylene bis-phosphines did form the open chaintris-phosphine catalys complexes of the present invention (Examples64-67). Overall, the stability of the complex solutions increased in theorder of their listing as indicated by their color stability. Commentson some of the details are made in the following.

The reaction mixture of methylene bis-diphenyl phosphine and the TPPcomplex was highly unstable (Example 61). Some of the TPP was displacedbut no single new complex predominated. The mixture rapidly turned dark.

The complex formed by the reaction of dimethylene bis-diphenyl phosphineexhibited a single doublet for the complexed phosphorus (Example 62).Based on the unusual chemical shift value of this doublet and theinstability of this mixture, the complex appeared to have a chelatingbis-phosphine moiety. The formation of this complex was apparentlycomplete, the ligand exchange is slow.

                                      TABLE 6                                     __________________________________________________________________________    .sup.31 P Nuclear Magnetic Resonance Parameter of Free                        and Rhodium Complexed Alkylene Bis-(Diphenyl Phosphines)                                                                 Coupling                                                                            Chemical Shift                                                Chemical Shift                                                                          Constant                                                                            Difference                   Example                                                                            Example                     O, ppm    PRh   ΔO, ppm                No. of                                                                             No. of                                                                             Chemical Structure     Free                                                                              Complexed                                                                           Complexed                                                                           Complex-                     Complex                                                                            Ligand                                                                             Complex of (RH(CO)H)   Ligand                                                                            Ligand                                                                              Ligand                                                                              Ligand                       __________________________________________________________________________    61   16   (Ph.sub.2 PCH.sub.2 PPH.sub.2)                                                                       -24.0                                        62   17                                                                                  ##STR56##             -14.0                                                                             +54.3 143   69.1                         63   18                                                                                  ##STR57##             -19.7                                        64   19   (Ph.sub.2 P(CH.sub.2).sub.4 PPh.sub.2).sub.3 Rh(CO)H                                                 - 18.4                                                                            +29.8 140   48.2                         65   20   (Ph.sub.2 P(CH.sub.2).sub.5 PPh.sub.2).sub.3 Rh(CO)H                                                 -18.5                                                                             +27.7 153   46.2                         66   21   (Ph.sub.2 P(CH.sub.2).sub.6 PPh.sub.2).sub.3 Rh(CO)H                                                 -18.3                                                                             +26.9 153   45.2                         67   22   (Ph.sub.2 P(CH.sub.2).sub.14 PPh.sub.2).sub.3 Rh(CO)H                                                -18.6                                                                             +27.5 152   46.1                         __________________________________________________________________________

The complex derived from the trimethylene bis-phosphine was of furtherincreased stability and reduced ligand exchange (Example 63). Based onthe complicated set of doublet signals, the presence of chelatingbis-phosphine complexes such as the compound shown in the table issuggested.

The complexing behavior and the nmr parameters of the non-chelatingpolymethylene bis-diphenyl phosphines (Examples 64-67) were, in general,very similar to that of the simple n-alkyl diphenyl phosphines. Moreparticularly, the ligand exchange rates observed were very similar tothose previously found for the SEP ligand. In the presence of excessligand, mostly one phosphine moiety of the bis-phosphine wascoordinated. The phosphine group at the other end was mostly free asindicated by the formulas of the table.

The ³¹ P nmr parameters of the rhodium complexes of ten variouslysubstituted alkyl diphenyl phosphines (Examples 68-78) were alsodetermined. With the exception of the diphenyl phosphine oxidesubstituted ligand (Example 72), all the complexes exhibited similarphosphorus to rhodium coupling constants. This indicated theirtris-phosphine complex character. In general these ligands exhibited thetype of behavior discussed previously in the case of trihydrocarbylsilylsubstituted alkyl diphenyl phosphines. Some specific observations aremade in the following.

The 2-phenylethyl diphenyl phosphine formed the usual tris-phosphinecomplex but was less effective than SEP in displacing TPP (Example 68).The next two ligands, i.e. the 2-pyrrolidinonyl and 3-diethylaminopropyldiphenyl phosphines, were similar to SEP both with regard to thecompleteness of the expected complex formation and ligand exchange(Examples 24, 25). It should be noted that the 2-pyrrolidinonylethylsubstitution led to unusual chemical shift values for both the free andcomplexed phosphine ligand.

                                      TABLE 7                                     __________________________________________________________________________    .sup.31 P NUCLEAR MAGNETIC RESONANCE PARAMETERS OF VARIOUSLY SUBSTITUTED      ALKYL                                                                         DIPHENYL PHOSPHINES AND THEIR RHODIUM COMPLEXES                                                                            Chemical                                                                Coupling                                                                            Shift                            Ex- Ex-                      Chemical Shift                                                                          Constant                                                                            Difference                       ample                                                                             ample                    σ, ppm                                                                            .sup.J P--Rh                                                                        Δσ, ppm              No. of                                                                            No. of                   Free                                                                              Complexed                                                                           Complexed                                                                           Complex -                                                                           Experimental No. E         Complex                                                                           Ligand                                                                            Chemical Structure of Complex                                                                      Ligand                                                                            Ligand                                                                              Ligand                                                                              Ligand                                                                              Ligand                                                                              Complex              __________________________________________________________________________    68  23  (Ph.sub.2 PCH.sub.2 CH.sub.2 Ph).sub.3 Rh(CO)H                                                     -16.6                                                                             +27.6 153   44.2  4275-VIA                                                                            4275-VIB             69  24                                                                                 ##STR58##           -23.0                                                                             +21.6 151   44.6  5382-VIIIA                                                                          5382-IXB             70  25  [Ph.sub.2 PCH.sub.2 CH.sub.2 CH.sub.2 N(C.sub. 2 H.sub.5).sub.2               ]Rh(CO)H             -17.8                                                                             +27.4 151   45.2  5433-VIIIA                                                                          5433-VIIIB           71  26  [Ph.sub.2 PCH.sub.2 CH.sub.2 SO.sub.2 C.sub.2 H.sub.5).sub.3                  Rh(CO)H              -18.6                                                                             +27.3 151   45.9  5431-VIIIA                                                                          5431-VIII            72  27  (Ph.sub.2 PCH.sub.2 CH.sub.2 POPh.sub.2).sub.3 Rh(CO)H                                             -13.7                                                                             +30.5 190         5421-IIIA                                                                           5421-IIIC            73  28  (Ph.sub.2 PCH.sub.2 CH.sub.2 COCH.sub.3).sub.3 Rh(CO)H                                             +17.1                                                                             +28.1 149   45.2  5391-XIIA                                                                           5391-XIIB            74  29  (Ph.sub.2 PCH.sub.2 CH.sub.2 CO.sub.2 CH.sub.3).sub.3 Rh(CO)H                                      -17.7                                                                             +27.9 151   45.6  5384-XA                                                                             5384-XB              75  30  (Ph.sub.2 PCH.sub.2 CH.sub.2 CH.sub.2 OH).sub.3 Rh(CO)H                                            -16.9                                                                             +27.8 154   44.7  4291-VA                                                                             4291-VB              76  31  [(Rh.sub.2 PCH.sub.2 CH.sub.2 CH.sub.2).sub.2 O].sub.3 Rh(CO)H                                     -17.5                                                                             +27.8 151   45.3  4295-XIIA                                                                           4295-XIIB            77  32  (Ph.sub.2 PCH.sub.2 CH.sub.2 CH.sub.2 SCH.sub.3).sub.3 Rh(CO)H                                     -17.7                                                                             +27.1 151   44.8  4296-VIIIA                                                                          4296-VIIIB           __________________________________________________________________________

The β-sulfone and β-phosphinoxide substituted ligands both completelydisplaced TPP like SEP did (Examples 71 and 72). However, they exhibiteda significantly lower ligand exchange rate at room temperature. Partlydue to the phosphine-phosphine oxide coupling, the spectrum of thephosphine oxide substituted complex appeared to be exceptional.

As far as the remaining ligands are concerned, the 2-carbomethoxyethylderivative also exhibited a smaller ligand exchange than SEP (Example74). The rest of the ligands were similar to SEP both with regard toequilibria and rates (Examples 73 and 75 to 77).

Other suitable substituted alkyl diaryl phosphines are reacted similarlywith tris-(triphenyl phosphine) rhodium carbonyl hydride,tris-(triphenyl arsine) rhodium carbonyl hydride and the like to providethe corresponding tris-phosphine complexes. For example, starting withthe substituted alkyl diphenyl phosphine ligands of Examples 33 to 47,the following miscellaneous substituted alkyl diphenyl phosphinecomplexes are formed:

    ______________________________________                                        Example No. 5                                                                 Complex                                                                              Ligand  Name of the Complex Formed                                     ______________________________________                                        78     33      tris-(naphthyl ethyl diphenyl phosphine)                                      rhodium carbonyl hydride                                       79     34      tris-(aminopropyl diphenyl phosphine)                                         rhodium carbonyl hydride                                       80     35      tris-(morpholinopropyl diphenyl phosphine)                                    rhodium carbonyl hydride                                       81     36      tris-(carbamylethyl diphenyl phosphine)                                       rhodium carbonyl hydride                                       82     37      tris-(carbazylethyl diphenyl phosphine)                                       rhodium carbonyl hydride                                       83     38      tris-(pyridylethyl diphenyl phosphine)                                        rhodium carbonyl hydride                                       84     39      tris-(phthalimidoethyl diphenyl phosphine)                                    rhodium carbonyl hydride                                       85     40      tris-(diethyoxyphosphonylethyl diphenyl                                       phosphine) rhodium carbonyl hydride                            86     41      tris-(ethoxypropyl diphenyl phosphine)                                        rhodium carbonyl hydride                                       87     42      tris-(2-propoxyethyl diphenyl phosphine)                                      rhodium carbonyl hydride                                       88     43      tris-(furylethyl diphenyl phosphine)                                          rhodium carbonyl hydride                                       89     44      tris-(acetoxypropyl diphenyl phosphine)                                       rhodium carbonyl hydride                                       90     45      tris-(benzoyloxyethyl diphenyl phosphine)                                     rhodium carbonyl hydride                                       91     46      tris-(phenylthiopropyl diphenyl phosphine)                                    rhodium carbonyl hydride                                       92     47      tris-[bis-(diphenylphosphinoethyl) sulfone]                                   bis-(rhodium carbonyl hydride)                                 ______________________________________                                    

Similar substituted alkyl diaryl phosphine complexes are prepared fromsubstituted alkyl difluorophenyl phosphines, substituted alkyl ditolylphosphines, and substituted alkyl phenyl naphthyl phosphines.

By selecting the appropriate substituent, the complex catalysts of thepresent invention can be fine tuned to provide optimum performance atthe desired temperature. Also, substitution could be used as a means ofadjusting the solubility character of the free and complexed alkyldiaryl phosphine ligands. For example, the hydrophilic-lipophiliccharacter of the ligand could be appropriately changed by introducingeither large hydrocarbon substituents (Example 3) or highly polar groups(Example 24). The acid-base character can be also changed. For example,a basic amino group could be introduced (Example 25). Such a group canbe the essential factor in catalyst recovery. Other ligand substituentscan increase the solubility of gaseous reactants such as CO in theliquid reaction medium. A multiplicity of non-chelating phosphine groupswill drastically reduce ligand volatility.

In general, it should be pointed out that a correlation of the nmr andcatalysis studies showed that those complexes which show lower ligandexchange rates at low temperatures have a higher activation energy ascatalyst. That means that they required more thermal activation, i.e.higher temperatures, to become highly active catalysts. Less ligandexchange also meant a higher temperature for the irreversible thermaldissociation, i.e. decomposition of the catalyst complex.

Under the preferred process conditions for the present catalysts, thestructure of the tris-(alkyl diphenyl phosphine) rhodium carbonylhydrides as described by the nmr parameters could be formed in situ anddid not undergo any irreversible change. For example, the tris-SEPcomplex was generated under routine hydroformylation conditions at 120°from dicarbonyl acetylacetonato rhodium and was employed for 1-butenehydroformylation. After the reaction was complete, the volatilecomponents were removed by distillation and the residual liquid wasstudied by ³¹ P nrm. The typical parameters for tris-SEP rhodiumcarbonyl hyride and excess free SEP were found.

General Method of Hydroformylation

The hydroformylation of butene-1 to provide linear pentanal and branched2-methyl butanal products was selected for comparative studies of thecatalytic properties of certain of the alkyl diaryl phosphine complexesof the invention. The complexes studied were either isolated before useor generated in situ. In some cases, the desired complex was generatedfrom the known tris-(triphenyl phosphine) rhodium carbonyl hydride bythe addition of the appropriate ligand in varying amounts. According toanother standard method, dicarbonyl acetylacetonato rhodium and theappropriate alkyl diaryl phosphine were used as catalyst precursors. Inthat case, the desired rhodium carbonyl hydride complex was generated byhydrogenation during the hydroformylation experiment. Tris-(triphenylphosphine) rhodium carbonyl hydride in the presence of varying excessesof triphenyl phosphine was used as a known catalyst standard forcomparison.

The experiments were carried out in a 300 ml stainless steel (S) and a300 ml Hastelloy (H) autoclave, respectively. Both autoclaves wereequipped with identical, highly effective, impeller type stirrers,operating at 750 rpm during the experimental runs. The other standardautoclave instrumentation was identical for both units. However, aslightly lower normal to iso aldehyde product ratio (n/i) was observedin unit H. In those casees where the type of autoclave was notspecified, a stainless steel unit was used.

The standard batch hydroformylation procedure was the following: theappropriate amounts of rhodium complex were dissolved in 100 g of theproper mixture of a free phosphine and solvent. 2-propylheptyl valerateof 2-ethylhexyl acetate were used as standard solvents. They wereindistinguishable. Most Often the amount of complex employed provided100 ppm rhodium concentration. This meant 100 mg, i.e., about 0.1 mmolerhodium per 100 g. Accordingly, 100 mg per Kg, about 1 mmole per kgrhodium would be present in 1 kg starting mixture. The excess ligandadded to the solvent was usually calculated to provide a ligand torhodium ratio (L/Rh) of about 140.

The 100 g rhodium complex-ligand solution was placed into the autoclavewhich was then deaerated by repeated pressurization with nitrogen. Thesolution under atomospheric nitrogen pressure was then sealed and heatedto the reaction temperature, usually 100° C.

When the solution reached 100° C., 20 g of liquid butene was pressuredinto the autoclave with a 1 to 4 carbon monoxide-hydrogen initial gasmixture. The butene was followed by the CO/H₂ mixture until a pressureof 350 psig was reached. At that point, the supply of 1:4 CO/H₂ was shutoff and the autoclave was connected to a cylinder to about 1 litervolume containing a 1:1 CO/H₂ feed gas mixture at 1000 psig. Theconnection was made through a pressure regulating valve set to providethe 1:1 CO/H₂ gas to the autoclave to maintain a 350 psig pressureduring the reaction. The exact H₂ /CO ratio of the feed gas was oftenvaried to maintain the initial H₂ /CO ratio in the autoclave.

In the standard tests, the autoclaves used were equipped with synthesisgas feed lines adjoining the autoclave above the Magnedrive stirrerassembly unit (FIG. 4). It is to be noted that this manner ofintroducing synthesis gas feed far from the upper level of the liquidreaction mixture resulted in an incomplete equilibriation of thesynthesis gas mixture between the gas and liquid phase. Particularly inthose cases where the initial synthesis gas mixture (used to pressure upthe reaction mixture) had an H₂ to CO ratio of 10 or higher, the COcomponent of the subsequent one to one feed gas was not effectivelydelivered from the top into the liquid reaction mixture due to masstransfer limitations. Therefore, the reaction mixture was often"starved" of CO during the early fast phase of the reaction. As aconsequence, the H₂ /CO ratio in the liquid temporarily rose to veryhigh values. This resulted in particularly high n- to i- aldehydeproduct ratios. Also, olefin hydrogenation and isomerization becameimportant side reactions. This, of course, reduced the absolute accuracyof the data on catalyst selectivities. For comparison, the widelystudied Tris-TPP rhodium carbonyl hydride catalyst system was used as astandard throughout the work.

In those instances, where the effect of H₂ to CO ratios and the effectof CO partial pressure were specifically studied, the synthesis gas feedwas introduced at the side of the autoclave, just above the liquidlevel. This method of operation largely avoided any temporary rise H₂/CO ratios and drastically reduced hydrogenation and isomerization incases where the initial H₂ /CO ratio was high. Special studies were alsomade in a continuous feed introduction and product flashoff operation.This allowed a continuos control of partial pressures and such providedthe most accurate results (FIG. 12).

The progress of the hydroformylation was followed on the basis of theamount of 1:1 CO/H₂ consumed. The latter was calculated on the basis ofthe pressure drop in the 1 liter CO/H₂ cylinder. Reactant conversioncalculated on the basis of CO consumption was plotted against thereaction time to determine the reaction rate. The reaction rate wasexpressed as the fraction of the theoretical CO/H₂ requirement consumedper minute (k min⁻¹). The reaction was discontinued when the reactionrate drastically dropped. Dependent on the side reaction, such asbutene-1 hydrogenation and butene-1 to butene-2 isomerization, thestability of the catalyst complex in the mixture, such a rate dropoccurred generally between 80-98% conversion. Accordingly, the reactionswere usually discontinued in that conversion range. Most often thereactions were run up to 80% conversion.

When the reaction was to be discontinued, the CO/H₂ feed valve was shutand the autoclave was immediately cooled with cool water. In case of lowconversions, ice bath was used. When cooling was complete, the synthesisgas was released slowly. The residual liquid was visually observed forcatalyst decomposition. A dark orange to brown color of the originallyyellow mixture indicated increasing degrees of catalyst decomposition.Severe catalyst decomposition usually resulted in the precipitation ofdark solids.

Analyses of the residual liquid mixture were carried out using gaschromatography. The liquids were analyzed in a gc instrument using flameionization detector. By this instrument, the C₄ hydrocarbons weredetected. Due to the lower response of this detector to the aldehydes,the intensity of the hydrocarbon peaks was multiplied usually by 0.7 toobtain the necessary concentration correction. The individual, gaseousC₄ hydrocarbons were separated by another chromatograph. At first thegases were separated from the liquids and then the individual componentsof the gas were chromatographed and detected by a thermal conductivitydetector.

1-Butene Hydroformylation Experiments (Examples 93-100)

In the following description of 1-butene hydroformylation catalysis bytris-(alkyl diaryl phosphine) rhodium carbonyl hydride based catalystsystems, at first their unique catalytic behavior will be exemplified bya detailed description of the tris-(trimethylsilylethyl diphenylphosphine) rhodium carbonyl hydride, i.e. SEP complex, plus SEP system.For comparison, detailed data will be also provided on the knowtris-(triphenyl phosphine) rhodium carbonyl hydride, i.e. TPP complex,plus TPP system. This will be followed by short descriptions of thecatalytic behavior of various substituted and unsubstituted alkyldiphenyl phosphines. Finally, an example of a continuoushydroformylation process based on the SEP system will be described.

EXAMPLE 93 Tris-(Trimethylsilylethyl Diphenyl Phosphine) RhodiumCarbonyl Hydride as a Catalyst in the Presence of 140-Fold Ligand Excessat Different Temperatures

The complex of Example 48 was studied at the 107 ppm rhodium level inthe presence of 140-fold trimethylsilylethyl diphenyl phosphine (SEP)ligand as a butene hydroformylation catalyst using the generalprocedure. Comparative experiments were run using 107 ppm rhodium as atris-(triphenyl phosphine) carbonyl hydride complex with 140-foldtriphenyl phosphine (TPP). Reaction rates, n/i product ratios,conversions and by-products were determined at various temperatures. Theresults are shown by Table 7.

The data of the table show that both the SEP and the TPP based catalystsystems are highly active and produce a high ratio of n/i products atmost temperatures. However, the temperature dependence of the twosystems is very different.

                                      TABLE 8                                     __________________________________________________________________________    HYDROFORMYLATION AT DIFFERENT TEMPERATURES                                    Feed: Butene-1 and 1:4 CO/H.sub.2 at 350 psi                                  Catalyst: L.sub.3 Rh(CO)H, Rh 107 ppm, Rh/L = 140                             SEP Ligand: (CH.sub.3).sub.3 SiCH.sub.2 CH.sub.2 PO.sub.2 TPP Ligand:         O.sub.3 P                                                                     Variable Conditions                                                                        Reaction Rates and Selectivities                                 of Catalysis                         By-Product,                                                                            Details                                 Reaction                                                                           Fraction of                                                                           Product                                                                            Reaction                                                                           Butene                                                                              Mole % in                                                                              Exact                                                                              Exp.                       Seq.                                                                             Catalyst                                                                           Temp.,                                                                             CO/H.sub.2 Reacted                                                                    n/i  Time Conversion                                                                          Product Mixture                                                                        Rh Conc.                                                                           Run                        No.                                                                              Ligand                                                                             °C.                                                                         k, min.sup.-1                                                                         Ratio                                                                              Min. %     Butane                                                                            Butene-2                                                                           ppm  No.                        __________________________________________________________________________    1  SEP  100  0.03    6.1  35   86.9   2.0                                                                               3.8 106  104                        2       120  0.10    6.2  35   96.5   9.4                                                                               6.2 106  110                        3       140  0.21    5.7  15   97.5  14.5                                                                              12.4 108  109                        4       145  0.27    5.0  15   95.2  11.9                                                                              12.1 109  115                        5  TTP  100  0.21    7.5  35   98.9  10.7                                                                              12.1 107  100                        6       120  0.34    5.9  10   97.3   9.3                                                                              12.2 104  112                        7       140  0.38    3.4  10   98.2  11.2                                                                              21.9 105  113                        8       145  0.27    2.4  15   97.7  11.9                                                                              26.0 103  114                        __________________________________________________________________________

The novel SEP catalyst system exhibits an increasing activity withelevated temperatures. At 100° C. and 120° C. the n/i ratio of productsis about the same and there is only a small n/i drop at 145° C. Highbutene conversion is observed at all temperatures. The only adverseeffect of temperature increase is the increased hydrogenation andisomerization of the butene-1 reactant. The SEP system remains clear,bright yellow in appearance, even at 145° C.

The known TPP catalyst system exhibits the same increased activity at120° C. and 140° C. However, the n/i ratios in this case aredramatically reduced with increasing temperatures. At 145° C., and n/iratio products is significantly lower in the TPP than in the SEP system.At 145° C., the reaction rate of the TPP system also drops.Decomposition of this system at this temperature is indicated bydarkening of the reaction mixture. The behavior of the SEP and TPPsystems is compared by FIGS. 5A and 5B.

The results of similar but more extensive studies are shown in FIGS. 6to 9. FIG. 6 correlates the hydroformylation rate with the temperature.It shows that in the presence of the SEP complex catalyst, the rates of1-butene hydroformylation were increasing with elevated temperatures upto 155° C. In the case of the TPP catalyst, increased rates wereobserved only to about 135° C. Beyond these temperatures, reducedhydroformylation rates were observed apparently due to catalystdecomposition.

FIG. 7 correlates the hydroformylation temperature with the selectivityfor producing the linear (n-) versus branched (i-) aldehyde. It is shownthat the n/i ratios depend on the temperature in the case of bothcatalysts.

When hydroformylations are carried out above the stable temperaturerange of the catalysts, a drastic drop in the n/i ratios is observed.This drop occurs above 165° C. for the SEP catalyst and above 135° C.for the TPP catalyst. At the same hydroformylation temperature, the useof the SEP catalyst leads to somewhat higher n/i ratios. It appears thatthe SEP catalyst could be used at an about 20° C. higherhydroformylation temperature than the TPP catalyst and would stillexhibit a selectivity equal to that of TPP at the lower temperature.

With regard to the undesired hydrogenation of the 1-butene feed toproduce n-butane (FIG. 8), it is noted that, in the case of the SEPcatalyst, the percentage of n-butane formed more than triples to about11% when the reaction temperature is increased from 100° C. to 135° C.However, there is very little increase between 135° C. and 165° C. Incontrast, limited data indicate that, in the case of the TPP catalyst,the level of hydrogenation stays around the 10% level between 100° C.and 140° C.

The behavior of the SEP and TPP catalysts appears to be also differentwith respect to the isomerization of the 1-butene feed to cis- andtrans-butene-2 by-products (FIG. 9). In general, less isomerizationoccurs when the SEP catalyst is used. However, the percentage ofisomerized olefin is increased with temperature in the presence of bothcatalysts, up to 165° C. When the SEP catalyst becomes unstable at 170°C., less 2-butenes by-products are obtained apparently due to secondaryreactions, i.e., hydrogenation and hydroformylation. In contrast, thethermal destabilization of the TTP catalyst in the 140°-145° rangeresults in a large increase of the percentage of 2-butenes in thereaction mixture.

Example 94 Tris-(Trimethylsilylethyl Diphenyl Phosphine) RhodiumCarbonyl Hydride as a Catalyst at Different Levels of Excess LigandConcentrations

The complex catalyst of Example 48 was studied mainly at the 105 ppmrhodium level and at 100° C. reaction temperature to determine theeffect of the excess trimethylsilylethyl diphenyl phosphine ligand(SEP). The SEP concentration used ranged from 5 to 149 mmole per liter.Some comparative experiments were also carried out using tris-(triphenylphosphine) rhodium carbonyl hydride and varying excess concentrations ofthe corresponding triphenyl phosphine ligand (TTP). The results of thesestudies are shown in Table 8.

The data of Table X show that, in general, increasing concentrations ofexcess ligand result in decreased reaction rates but sharply increasedselectivities, i.e., n/i ratios, in both the novel and the knowncatalyst systems. There is an apparent inhibition and stabilization ofboth systems at high ligand concentrations. However, the behavior of thetwo catalysts is significantly different at relatively low excess ligandconcentrations.

                                      TABLE 8                                     __________________________________________________________________________    HYDROFORMYLATION AT DIFFERENT LEVELS OF EXCESS LIGAND CONCENTRATIONS                        Feed: Butene-1 and 1:4 CO/H.sub.2 at 350 psi                                  Catalyst: L.sub.3 Rh(CO)H                                                     SEP Ligand: (CH.sub.3).sub.3 SiCH.sub.2 CH.sub.2 PO.sub.2                     TPP Ligand: O.sub.3 P                                           Variable Conditions of Catalysis   Reaction Rates and Selectivities                             Excess Rhodium                                                                            Ligand to                                                                          Fraction of                                                                           Product                                                                            Reaction                                                                           CO Con-                  Seq.                                                                             Catalyst                                                                           Reaction                                                                            Auto-                                                                             Ligand Conc.                                                                         Conc.                                                                              Rh Ratio                                                                           CO/H.sub.2 Reacted                                                                    Linearity                                                                          Time version                  No.                                                                              Ligand                                                                             Temp. °C.                                                                    Clave                                                                             mMole/lit.                                                                           ppm  L/Rh k min-1 Ratio, n/i                                                                         min. %                        __________________________________________________________________________    1  SEP  100   H    5     105  5.2  0.24    3.5  20   88.7                     2                 24     105  24.2 0.09    4.0  35   87.1                     3             S   28     105  28   0.12    4.4  35   88.0                     4                 56     217  28   0.12    5.4  30   94.2                     5                 143    105  143  0.03    6.1  35   83.6                     6       120   S   29     105  29   0.30    4.5  15   93.0                     7                 60     210  30   0.25    5.7  15   89.6                     8                        149  105  0.10    6.2  35   88.1                     9  TPP  100   H    5     105  5    0.28    3.0  15   80.8                     10                142    102  142  0.17    3.8  35   96.5                     11            S   27     105  27   0.31    4.7  15   86.6                     12                143    104  143  0.03    6.1  35   83.6                     __________________________________________________________________________

The novel SEP catalyst system leads to higher n/i product ratio than theTPP system at five mmole/l excess ligand concentration (Seq. No. 1 vs.Seq. No. 9). At the intermediate SEP concentration of 56 mmole, there isa good selectivity and sufficient reaction rate (Seq. No. 4). It isinteresting to observe that the positive effect of increasing catalystcomplex concentration on the reaction rate can be counter-balanced bythe inhibiting effect of increased SEP concentration (compare Seq. Nos.3 vs. 4 and 6 vs. 7). Clearly, the SEP concentration is more importantthan the SEP/Rh ratio. AT the high SEP level of 143, there is somefurther increase in the n/i ratio, but reaction rate is cut to about onefourth (compare Seq. Nos. 4 and 5). At this level, the rate can beincreased while maintaining the high n/i ratio by increasing thereaction temperature (see Seq. No. 8 and the table of the previousexample).

The effect of different ligand to rhodium ratios on the n/i ratios ofbutene hydroformylation at different temperatures was further examined.The results are summarized by FIG. 10.

The figure shows that as the SEP/Rh ratio changes from about 140 toabout 1000, the n/i ratios at 80% conversion changes from about 2 to 7.The major change in the percentage of the n-aldehyde product occurs inthe 140 to 500 L/Rh range. It was shown in additiional experiments thatthere was very little further selectivity increase when the SEP ligandwas used as the solvent (i.e., in about 75% concentration).

The increased selectivity to linear aldehyde is a consequence of theincreased catalyst stability in these experiments. The increasedcatalyst stability is also reflected in a decreasing darkening of thereaction mixture with increasing ligand concentration. Another sign ofthe increased stability is the better maintenance of thehydroformylation rate with increasing conversion. Finally, it was alsonoted that the increased ligand concentration resulted in a moderatesuppression of the rate of hydrogenation. Nevertheless, hydrogenationremained significant enough to cause a decreasing H₂ /CO ratio duringthe reaction.

Similar studies of the effect of increased SEP/Rh ratio were carried outat 160°, 145° and 120° C. The data obtained at 145° are also shown inFIG. 10. The lower the reaction temperature, the less effect ofincreased L/Rh ratios was observed. At decreasing temperatures, most ofthe effects were observed in the range of increasingly low L/Rh ratios.Also, the main effect was on selectivity rather than on stability.

Example 95 Hydroformylation Selectivity of Tris-(TrimethylsilylethylDiphenyl Phosphine) Rhodium Carbonyl Hydride Excess Ligand CatalystSystem at Different Olefin Conversions, i.e. At Different CarbonMonoxide Concentrations

Butene-1 was hydroformylated in the Hastalloy unit according to thegeneral procedure. The catalyst and ligand concentrations were higherthan usual and the reaction conditions milder as shown in Table 9. Thereaction mixture was frequently sampled during the process and thesamples were analyzed by gc to determine the relative selectivities ton- and i- aldehyde products and hydrocarbon by-products as a function ofbutene-1 conversion. The detailed data are given in Table 9.

The data of Table 9 indicate that the n- to i-ratio of aldehydes in thereaction is decreasing as the conversion increases. Up to about 60%butene conversion, the n/i ratio stays above 18.5, although it issteadily dropping (see Sample Nos. 1-2). In the 72-78% conversion range,the n/i ratio is about 14. Once butene-1 conversion reaches 90%, the n/iratio of the product mixture is down to about 11.5.

                                      TABLE 9                                     __________________________________________________________________________    HYDROFORMYLATION SELECTIVITY AT DIFFERENT OLEFIN CONVERSION LEVELS                     Feed: Butene-1 and 1:4 CO/H.sub.2 at 130 psi at 110° C.                under 130 psi                                                                 Catalyst: L.sub.3 RH(CO)H, Rh 212 ppm, L Excess 300 mMole, L/Rh               140                                                                           L: OPCH.sub.2 CH.sub.2 Si(CH.sub.3).sub.3                            Conversion Related Data  Aldehyde                                                                           Mole % Selectivity to Various Compounds             Butene-1                                                                            Conversion %                                                                            Reaction                                                                           Product                                                                            Aldehyde                                                                            Butane  2-Butene                          Sample                                                                            Conversion                                                                          Based on  Time,                                                                              Linearity                                                                          Products                                                                            Hydrogenation                                                                         By-Products                       No. %     CO/H2 Consumed                                                                          Min. Ratio, n/i                                                                         n  i  Product cis                                                                              trans                          __________________________________________________________________________    1   26.4  21.9      10   26   68.4                                                                             2.7                                                                              11.9    9.7                                                                              7.3                            2   46.9  36.0      15   25   77.9                                                                             3.1                                                                              7.4     6.7                                                                              4.9                            3   61.6  50.0      20   18.5 79.7                                                                             4.3                                                                              6.1     5.8                                                                              4.2                            4   72.0  61.4      25   13.9 80.2                                                                             5.8                                                                              5.2     5.2                                                                              3.7                            5   78.0  69.4      30   14.0 79.6                                                                             5.7                                                                              5.4     5.4                                                                              3.9                            6   90.0  79.9      40   11.6 82.1                                                                             7.1                                                                              3.9     4.0                                                                              2.9                            7   90.5  87.9      60   11.3 81.9                                                                             7.2                                                                              4.0     4.0                                                                              3.0                            __________________________________________________________________________

It was also observed that during the conversion of about 25% of thebutene, the total aldehydes to hydrocarbon by-products ratio was lowerthan at higher conversions (about 70/30 versus 90/10). It is believedthat this is due to uncontrolled nonequilibrium conditions early duringthe reaction. Almost all the hydrogenation occurred during the first 10minutes of the reaction. During the early, very fast part of thereaction, the liquid reaction medium became starved of CO. Due to theresulting low CO partial pressure, the n/i product ratio became veryhigh. However, the amount of CO during some of this period was soinsufficient that much hydrogenation and isomerization occurred. In acontinuous process, where the low optimum concentration of CO could bemore accurately maintained, high selectivity to aldehydes could bebetter achieved without producing significant amounts of by-products.

Example 96 Hydroformylation with the Tris-(Trimethylsilylethyl DiphenylPhosphine) Rhodium Complex System

In a series of experiments, tris-(triphenyl phosphine) rhodium carbonylhydride was reacted with a varying excess concentration of the novelsubstituted diaryl alkyl phosphines. This resulted in the formation ofthe novel catalysts of the present invention which were studied fortheir catalytic properties in the usual manner in the Hastalloy unit(H).

Tris-(triphenyl phosphine) rhodium carbonyl hydride, 0.1 g (0.1 mmole),was mixed with 80 g of a mixture of 4 g (14 mole) of trimethylsilylethyldiphenyl phosphine and 76 g 2-propylheptyl valerate to provide an SEPcatalyst system. For comparison, the same complex was also mixed with 80g of a mixture of 3.7 g (14 mole) of triphenyl phosphine to provide aTPP catalyst system. This provided two systems having 105 ppm rhodiumand a 140 fold ligand excess.

Butene hydroformylations were then carried out with both catalystsystems at 100° C. in the usual manner. The results indicated that themain catalytic species of the SEP system is a SEP complex. The reactionrate of the SEP system was about 1/6 of the TPP system (k min⁻¹ valuesof 0.02 and 0.12, respectively). The n/i product ratios were about thesame (4.2).

Other SEP catalyst systems were made up the same way except for thedifferent L/Rh ratios: 25 and 5. They were also employed successfullyfor butene hydroformylation.

Example 97 Hydroformylation with the Tris-(Trimethylsilylethyl DiphenylPhosphine System at Different H₂ /CO Ratios

For a further study of the effect of the H₂ /CO ratios onhydroformylation selectivity, the feed gas was provided through the sidearm of the autoclave to provide conditions during the reaction which arecloser to equilibrium. This type of operation was specific to thisexample.

The SEP complex catalyst was formed in situ during hydroformylation fromacetylacetonato dicarbonyl rhodium. The H₂ /CO ratios of both theinitial H₂ /CO gas and the final unreacted synthesis gas, in the headspace of the autoclave, were analyzed. The H₂ CO ratio of the feed gaswas adjusted to keep the initial and final H₂ /CO ratios the same asmuch as possible.

The results are shown by Table 10. The data show that as the H₂ /COratio was increased from 1 to 20 the ratio of n- to i- aldehydes wasincreased. It is also interesting to note that having the side arm feedresulted in much less 1-butene isomerization and hydrogenation thanobtained previously with top feeding.

                                      TABLE 10                                    __________________________________________________________________________    1-BUTENE HYDROFORMYLATION WITH SYNTHESIS GAS OF VARYING H.sub.2 /CO RATIO     IN THE PRESENCE OF                                                            SEP COMPLEX AND TPP COMPLEX CATALYSTS                                                       Total Pressure 350 psi (260 Atm.); Catalyst: L.sub.3                          Rh(CO)H; L/Rh = 140, Rh = 110 ppm                                             Solvent: 2-Ethylhexyl Acetate                                                       CO Partial                                                                          Fraction of   Aldehyde                                     Reac-        Pressure                                                                            H.sub.2 /CO Reacted                                                                     Reac-                                                                             Product  Selectivities to                    tion                                                                              H.sub.2 /CO Ratio                                                                      pCO, psi                                                                            Rate Conver-                                                                            tion                                                                              Linearity                                                                              Various Compounds, %         Seq.   Temp.                                                                             Ini-     Ini-  Constant                                                                           sion Time,                                                                             Ratio                                                                             100 n %                                                                            Aldehydes 2-                 No.                                                                              Ligand                                                                            °C.                                                                        tial                                                                             Feed                                                                             Final                                                                            tial                                                                             Final                                                                            k, min.sup.-1                                                                      %    Min.                                                                              n/i n + i                                                                              n  i  Butane                                                                            Butene             __________________________________________________________________________    1  SEP 120 1.18                                                                             1.08                                                                             1.36                                                                             160                                                                              149                                                                              0.115                                                                              81   13  3.09                                                                              7.56 73.7                                                                             23.8                                                                             0.6 1.8                2  SEP 120 5.0                                                                              1.08                                                                             4.8                                                                              59 60 0.082                                                                              81   22  4.56                                                                              8.20 78.2                                                                             17.1                                                                             1.7 2.9                3  SEP 120 10.0                                                                             1.08                                                                             7.8                                                                              31 39 0.090                                                                              82   30  6.60                                                                              86.8 80.8                                                                             12.2                                                                             2.8 3.2                4  SEP 120 15.0                                                                             1.17                                                                             10.4                                                                             22 30 0.116                                                                              81   15  8.22                                                                              89.2 80.4                                                                              9.8                                                                             4.4 5.3                5  TPP  90 1.08                                                                             1.08                                                                             1.8                                                                              168                                                                              125                                                                              0.060                                                                              81   29  3.76                                                                              79.0 77.0                                                                             20.5                                                                             0.8 1.7                6  TPP  90 5.0                                                                              1.08                                                                             9.0                                                                              59 35 0.059                                                                              81   28  5.50                                                                              84.6 80.5                                                                             14.7                                                                             1.2 3.6                7  TPP  90 10.0                                                                             1.08                                                                             10.5                                                                             31 30 0.062                                                                              80   26  6.70                                                                              87.0 81.0                                                                             12.1                                                                             2.0 4.8                8  TPP  90 15 1.17                                                                             18 22 18 0.062                                                                              80   26  8.70                                                                              89.7 80.2                                                                              9.2                                                                             4.6 6.0                __________________________________________________________________________

Comparative side arm feed experiments were also carried out using theknown TPP catalyst system at the same concentration. At 120° C.,significant side reaction continued to occur. Apparently, equilibriumconditions were not sufficiently approached. Consequently, furtherexperiments were carried out at 90° C. where the reaction rate issufficiently slow to avoid side reactions. The results are also shown inTable 10. They show that TPP at 90° C. exhibits a similar behavior tothat of SEP at 120° C. The n/i ratios are slightly higher for TPP,apparently due to a higher average of H₂ /CO ratios.

Example 98 Hydroformylation with the Tris-(Trimethylsilylethyl DiphenylPhosphine Rhodium Complex System at Different CO Partial Pressures

The results of the type of experiments described in Example 97 wereplotted in FIG. 11 to show the dependence of n/i aldehyde product ratioson the CO partial pressures. In additional experiments the H₂ /CO ratioswere kept constant with changing CO partial pressures by maintaining anappropriate fraction of the total 350 psi (26 Atm.) gas pressure by N₂gas. There was relatively little change in reaction rates.

FIG. 10 shows that decreasing CO partial pressures result in higher n/iproduct ratios even though the H₂ /CO ratio is kept constant. Thedependence of the n/i ratios is particularly strong in the low COpartial pressure range.

Example 99 Comparative Hydroformylation withTris-(Trihydrocarbylsilylalkyl Diphenyl Phosphine) Carbonyl HydrideBased Catalyst Systems

In a series of experiments, the results of which are shown in Table 11,various silyl substituted alkyl diphenyl phosphine complexes were testedas 1-butene hydroformylation catalysts under standard test conditions,using top synthesis gas feed.

                                      TABLE 11                                    __________________________________________________________________________    1-BUTENE HYDROFORMYLATION IN THE PRESENCE OF VARIOUS TRIS(SILYL               SUBSTITUTED                                                                   ALKYL DIPHENYL PHOSPHINE) RHODIUM CARBONYL HYDRIDE COMPLEX CATALYSTS                              Catalyst: L.sub.3 Rh(CO)H, Rh = 107 ppm, L/Rh = 140                           Pressure: 350 psi (26 Atm)                                L = Ph.sub.2 PR; R.sub.1 = CH.sub.2 CH.sub.2 SiC.sub.3 H.sub.7 ; R.sub.2      = CH.sub.2 CH.sub.2 SiPh.sub.3 ; R.sub.3 = [Ph.sub.2 PCH.sub.2 CH.sub.2       ].sub.2 Si(CH.sub.3).sub.2 ;                                                  R.sub.4 = CH.sub.2 CH.sub.2 CH.sub.2 Si(CH.sub.3).sub.3 ; R.sub.5 =           CH.sub.2 Si(CH.sub.3).sub.3                                                          Ex-                                       Selectivity to                      ample                                                                             Reac-               Con-                                                                             Reac-          Various Compounds, %                No. of                                                                            tion           Rate ver-                                                                             tion           Aldehyde                     Seq. No.*                                                                        Ligand LR                                                                         Com- plex                                                                         Temp.  °C.                                                                 H.sub.2 /CO Ratios InitialFeedFinal                                                      Constant k, min.sup.-1                                                             sion %                                                                           Time Min.                                                                         Ratio n/i                                                                          ##STR59##                                                                           Products,                                                                            Bu- tane                                                                         2-Bu- tene         __________________________________________________________________________    1a LR.sub.1                                                                          49  120 5   1.08                                                                              3.6                                                                              0.072                                                                              80 30  8.90                                                                              89.9   63.4                                                                              7.1                                                                              20.2                                                                             9.3                1b LR.sub.1                                                                          49  145 5   1.27                                                                              3.8                                                                              0.274                                                                              80  8  9.62                                                                              90.6   61.1                                                                              6.4                                                                              18.4                                                                             14.3               2  LR.sub.2                                                                          50  145 5   1.27                                                                              7.1                                                                              0.132                                                                              80 30  7.59                                                                              88.4   73.6                                                                              9.7                                                                               8.3                                                                             8.3                3  LR.sub.2                                                                          51  145 ˜4                                                                          ˜1                                                                          -- 0.157                                                                              80 12  7.6 88.4   --  -- -- --                 4a LR.sub.4                                                                          52  120 5   1.03                                                                              3.7                                                                              0.069                                                                              81 34  8.34                                                                              89.3   69.9                                                                              8.4                                                                              13.2                                                                             8.5                4b LR.sub. 4                                                                         52  145 4   ˜1                                                                          2.3                                                                              0.260                                                                              82  9  5.80                                                                              85.3   67.6                                                                              11.7                                                                             10.9                  5  LR.sub.5                                                                          53  100 5   1.05                                                                              5  0.056                                                                              78 60  6.24                                                                              86.2   54.3                                                                              8.1                                                                              31.8                                                                             5.9                __________________________________________________________________________     *Experiments of Seq. No. 1a and 1b were carried out in 2ethylhexyl acetat     as a solvent. The rest were in 2propylheptyl valerate.                   

The data indicate, that with the exception of the last catalyst, thecomplexes tested show the same type of catalyst behavior as thepreviously discussed SEP complex. The last complex tested, i.e., the onebased on the trimethylsilylmethyl ligand, was unstable. It showed lessselectivity than the others even at the relatively low hydroformylationtemperature used in this case.

Example 100 Hydroformylation with Various Tris(Alkyl Diphenyl Phosphine)Rhodium Carbonyl Hydride Catalysts

In a series of standard experiments, the results of which are shown inTable 12 various tris-(alkyl diphenyl phosphine) rhodium complexes wastested as 1-butene hydroformylation catalysts. It is emphasized that a 4to 5 H₂ /CO ratio and a 140 L/Rh ratio was used in these tests, incontrast to published work with similar systems.

Overall, all of the n-alkyl diphenyl phosphine complexes exhibitedsimilar catalytic behavior (Seq. Nos. 1-11). At sufficiently elevatedtemperatures, where they were active and stable, highly linear aldehydeproducts were selectively produced at a high rate. This is in contrastto the published low temperature results by Sanger and others which werereferred to earlier.

It is noted that the ligand volatility in the ethyl-, propyl- and butyl-diphenyl phosphine complex systems was found to be too high for theirapplication in a continuous product flashoff process. In contrast, theligand of the novel tris-(hexyl diphenyl phosphine) rhodium complexshowed no objectionable volatility (see Example 110). Other C₆ or higheralkyl substituents of appropriate structure can also provide the desiredreduced volatility.

                                      TABLE 12                                    __________________________________________________________________________    1-BUTENE HYDROFORMYLATION IN THE PRESENCE OF VARIOUS TRIS (ALKYL DIPHENYL     PHOSPHINE)                                                                    RHODIUM CARBONYL HYDRIDE CATALYSTS                                            __________________________________________________________________________    Catalyst: L.sub.3 Rh(CO)H, L/Rh = 140; Rh = 140 ppm; Percursor Dicarbonyl     Acetylacetonate Rhodium,                                                      Total Pressure 350 psi (˜26 Atm)                                        L: Ph.sub.2 PR; R.sub.1 = CH.sub.2 CH.sub.3 ; R.sub.2 = (CH.sub.2).sub.2      CH.sub.3 R.sub.3 = (CH.sub.2).sub.3 CH.sub.3 ; R.sub.4 = CH(CH.sub.3)C.sub    .2 H.sub.5 ;                                                                  R.sub.5 = CH.sub.2 CH.sub.2 C(CH.sub.3).sub.3 ; R.sub.6 = CH.sub.2            C(CH.sub.3).sub.3.                                                                                  Fraction of    Aldehyde   Selectivity to                        Reac-         H.sub.2 /CO Reacted                                                                          Product    Various Compounds                     tion          Rate Cover-                                                                             Reaction                                                                           Linearity  Aldehyde                       No.Seq.*                                                                          LR'Ligand                                                                         °C.Temp.                                                                    InitialFeedFinalH.sub.2 /CO Ratio                                                      k, min.sup.-1Constant                                                              %sion                                                                              Min.Time                                                                           n/iRatio                                                                          ##STR60##                                                                            niProducts                                                                          Butane                                                                            2-Butenes          __________________________________________________________________________     1  LR.sub.1                                                                          120 4.9 1.041                                                                            4.6                                                                              0.045                                                                              80   41   8.39                                                                              89.4   75.8                                                                             9.0                                                                              9.7 5.5                  2      145 4.9 1.041                                                                            2.8                                                                              0.113                                                                              80   19   6.38                                                                              86.5   66.0                                                                             10.4                                                                             12.3                                                                              11.3                 3  LR.sub.2                                                                          120 4.9 1.041                                                                            3.6                                                                              0.251                                                                              81   10   11.57                                                                             92.1   68.4                                                                             5.9                                                                              16.9                                                                              8.8                  4      145 4.9 1.041                                                                            2.6                                                                              0.326                                                                              81   6.5  5.92                                                                              85.6   63.9                                                                             10.8                                                                             12.9                                                                              12.4                 5      170 4.9 1.041                                                                            2.0                                                                              0.210                                                                              80   55   1.92                                                                              65.8   70.0                                                                             26.0                                                                             15.6                                                                              8.5                  6  LR.sub.3                                                                          145 4.9 1.174                                                                            3.8                                                                              0.337                                                                              80   6.0  7.15                                                                              87.7   62.4                                                                             8.7                                                                              15.5                                                                              13.4                 7  LR.sub.4                                                                          120           0.244                                                                              89   15   3.14                                                                               75.86                                8  LR.sub.5                                                                          120 4      2.7                                                                              0.114                                                                              80   15   7.57                                                                              88.3   74.3                                                                             9.8                                                                              8.6 7.4                  9      145 4         0.285                                                                              82   8    6.21                                                                              86.1   70.3                                                                             11.3                                                                             8.8 9.5                 10  LR.sub.6                                                                          120 4.9 1.083                                                                            3.0                                                                              0.224                                                                              81   14   4.82                                                                              82.8   59.2                                                                             12.3                                                                             16.7                                                                              11.8                11      145 4.9 1.083                                                                            2.8                                                                              0.361                                                                              80   6.5  3.15                                                                              75.9   53.8                                                                             17.1                                                                             7.4 21.7                __________________________________________________________________________     *The generally used solvent was 2propylheptyl valerate. In Seq. No. 6         2ethylhexyl acetate was used.                                            

In the second group of test results shown in Table 12, the effect ofalkyl substituents of different branching was investigated (Seq. Nos.7-11). Compared to the n-butyl derivative, the secondary butylderivative was found to be a much less selective catalyst for linearaldehyde production (Seq. No. 7). This is an apparent result of thesteric inhibition of the desired tris-phosphine complex formation (seeExample 56 for the nmr characteristics of the complex). It is also notedthat the t-butyl diphenyl phosphine system showed no catalytic activitywhatsoever under these condition. It is recalled that in that case notris-phosphine was formed at all (see Example 57 for attemptedcomplexing).

The last pair of ligands tested shows that minor structural differencescan result in major differences in the selectivity of the catalystsystem. The use of 3,3-dimethylbutyl diphenyl phosphine ligand, thecarbon analog of SEP, resulted in the desired high n/i ratio ofaldehydes (Seq. Nos. 8 and 9). This ligand does form tris-phosphinecomplex (see Example 59 for complex). In contrast, employing a neopentylgroup having one less methylene group between the phosphorus and thesterically demanding t-butyl group led to much poorer catalystselectivity (Seq. Nos. 10 and 11). This is again a consequence of thesteric inhibition of tris-phosphine formation (see Example 60).

Example 101 Hydroformylation with Chelating and Non-Chelating AlkyleneBis-(Diphenyl Phosphine) Rhodium Complex Catalysts

In a series of experiments, the results of which are summarized in Table13 alkylene bis(diphenyl phosphines) were tested as ligands for rhodiumcomplex catalyzed hydroformylation under standard conditions.

                                      TABLE 13                                    __________________________________________________________________________    1-BUTENE HYDROFORMYLATION IN THE PRESENCE OF CHELATING AND NON-CHELATING      ALKYLENE BIS-(DIPHENYL PHOSPHINE) RHODIUM COMPLEX CATALYSTS                   Rh = 140 ppm; Catalyst Precusor: Dicarbonyl Acetyl Acetonato Rhodium,         Total Pressure 350 psi (˜26 Atm)                                                                    Fraction of  Aldehyde Selectivity to              Ph.sub.2 P(CH.sub.2).sub.n PPh.sub.2 Ligand                                                  Reac-        H.sub.2 /CO Reacted                                                                    Reac-                                                                             Product Linearity                                                                      Various Compounds, %         Seq.* No.                                                                       Li- gand n                                                                       Complex Exp. No. E-                                                                 Ratio L/Rh                                                                       tion Temp. °C.                                                             H.sub.2 /CO Ratio Ini- tialFeedFinal                                                   Rate Constant k, Min.sup.-1                                                        Con- ver- sion, %                                                                 tion Time Min.                                                                      Ratio n/i                                                                        ##STR61##                                                                         Alde- hydes ni                                                                       Bu- tane                                                                         2-Bu-             __________________________________________________________________________                                                               tenes              1  1  61   1.5 120 5  1.08                                                                             5.8                                                                              0.025                                                                              78  135 2.1 67.7 47.1                                                                             22.4                                                                             2.9                                                                              27.6               2  1       71  120 4        Nil  Nil                                          3  2  62   1.5 120 5  1.08                                                                             4.1                                                                              0.067                                                                              80  45  1.5 60.6 42.9                                                                             22.8                                                                             7.6                                                                              21.8               4  2       69  145 4        Nil  Nil                                          5  3  63   1.5 120 5  1.08                                                                             3.6                                                                              0.120                                                                              80  30  2.0 66.2 45.6                                                                             23.3                                                                             9.5                                                                              21.6               6  3       73  120 5  1.08                                                                             5.9                                                                              0.030                                                                              80  65  1.3 56.5 52.1                                                                             40.2                                                                             4.5                                                                               3.2               7  4  64   69  145 4        0.190                                                                              81  11  3.3 76.5                             8  6  66   1.5 120 5  1.08                                                                             3.5                                                                              0.139                                                                              81  15  4.1 80.4 63.3                                                                             15.5                                                                             9.7                                                                              11.5               9  6       70  120 5  1.08                                                                             3.7                                                                              0.108                                                                              80  17  9.7 90.6 81.7                                                                              8.4                                                                             5.8                                                                               4.1               10 6       70  145 4  1.17                                                                             3.3                                                                              0.332                                                                              81   6  8.0 88.9 64.4                                                                              8.1                                                                             13.9                                                                             13.6               11 6       70  170 4  1.17                                                                             2.7                                                                              0.284                                                                              79  20  3.1 75.6 52.2                                                                             16.8                                                                             14.4                                                                             16.6               13 14 67   144 100 4        0.060                                                                              54      3.8 79.2                             __________________________________________________________________________     *Experiments of Seq. No. 538 and 4 were carried out in 2propylheptyl          valerate, the rest in 2ethylhexyl acetate.                               

The ligand to rhodium ratio was either 1.5 or about 70. Since these arebis-phosphine ligands, the above values correspond to a P/Rh ratio of 3and 140, respectively.

The bis-phosphine ligands tested had an increasing number (n) ofmethylene, i.e., CH₂ groups, separating the two phosphorus atoms. Thisincrease led to unexpected changes in catalysis.

In the case of the sterically crowded monomethylene (n=1) bis-phosphine,the catalyst system showed little activity and n/i selectivity at theL/Rh ratio of 1.5 and no activity at L/Rh ratio of 71 (Seq. Nos. 1 and2). The chelate forming dimethylene (n=2) bis-phosphine showed a similarbehavior (Seq. Nos. 3 and 4).

The trimethylene (n=3) bis-phosphine ligand, which forms a differentchelate (see Example 63), is more active that the previous ligands. Ithas significant activity when the L/Rh ratio is 1.5 (Seq. No. 5).However, as compared to the previous ligands, it has less activity andless selectivity when the L/Rh ratio is 73 (Seq. No. 6).

In contrast to the chelating bis-phosphines, the non-chelatingpolymethylene (n=4, 6, 14) bis-phosphines showed higher n/i productratios at the higher L/Rh ratio (Seq. Nos. 7 to 13). The catalyticbehavior of these bis-phosphine ligands, which form tris-phosphinecomplexes at high L/Rh ratios, is shown in detail in the case of thehexamethylene (n=6) compound. As can be seen at a 1.5 L/Rh ratio thehexamethylene bridged bis-phosphine ligand leads to an n/i aldehydeproduct ratio of 4.1. At a L/Rh ratio of 70, the n/i ratio is increasedto 9.7 under otherwise identical conditions.

Example 102 Hydroformylation with Aryl, Amide and Amine SubstitutedAlkyl Diphenyl Rhodium Complex Catalysts

In a series of standard 1-butene hydroformylation experiments, threesubstituted alkyl diphenyl phosphines representing aryl, amide and aminefunctionalities were studied as tris-phosphine rhodium complex formingligands. The results are shown in Table 14. As shown therein, all threecomplexes were highly selective catalysts for linear aldehydes whenstable. As the reaction temperature was increased beyond the stablerange of the desired catalyst complexes, the selectivities, i.e. n/ialdehyde ratios, decreased.

As described, the tests show that the novel 2-phenylethyl-,2-pyrrolidinonylethyl- and 2-diethylaminoethyl-diphenyl phosphinerhodium complexes previously described in Examples 68, 69 and 70 areselective catalysts in the hydroformylation of the present invention.

Example 103 Hydroformylation with Sulfone, Phosphine Oxide, Keto,Carboxylate, Hydroxy and Ether Substituted Alkyl Diphenyl RhodiumComplex Catalysts

The series of standard butene-1 hydroformylation tests summarized inTable XVII, describe the catalytic behavior of further, variouslysubstituted alkyl diphenyl phosphine rhodium complexes. As it wasdescribed in Examples 71 to 73 these complexes are all of thetris-phosphine type. The data of Table 15 show that they are allselective catalysts for forming highly linear aldehydes.

                                      TABLE 14                                    __________________________________________________________________________    BUTENE HYDROFORMYLATION IN THE PRESENCE OF ARYL, AMIDE AND AMINE              SUBSTITUTED ALKYL                                                             DIPHENYL PHOSPHINE RHODIUM COMPLEX CATALYSTS                                  Catalyst: L.sub.3 RH(CO)H; L/Rh = 140 Rh = 110 ppm; Precursor: Dicarbonyl     Acetylacetonato Rhodium;                                                      Total Pressure 350 psi (˜26 Atm); Solvent 2-Propylheptyl Valerate        ##STR62##                                                                                                              Aldehyde                                                                      Product                                                                       Linearity                                                                             Selectivity to                     Example                                                                            Reaction       Rate Conver-                                                                            Reaction 100 n,                                                                            Various Compounds, %        Seq.                                                                             Ligand                                                                            No. of                                                                             Temp.                                                                              H.sub.2 /CO Ratio                                                                       Constant                                                                           sion,                                                                              Time Ratio                                                                             n + i                                                                             Aldehydes                   No.                                                                              L   Complex                                                                            °C.                                                                         Initial                                                                           Feed                                                                             Final                                                                            k,Min.sup.-1                                                                       %    Min. n/i %   n  i Butane                 __________________________________________________________________________                                                         2-Butenes                1  L.sub.1                                                                           68   120  4.9 1.04                                                                             2.7                                                                              0.087                                                                              81   24   11.3                                                                              91.9                                                                              73.8                                                                             6.5                                                                              12.1                                                                              7.6               2           145  4.9 1.04                                                                             1.9                                                                              0.243                                                                              78   12   6.4 86.5                                                                              62.2                                                                             9.7                                                                              14.3                                                                              13.9              3           170  4.9 1.04                                                                             1.8                                                                              0.274                                                                              80   55   1.9 65.0                                                                              48.9                                                                             26.3                                                                             15.4                                                                              9.4               4  L.sub.2                                                                           69   100  4.9 1.04                                                                             10.2                                                                             0.011                                                                              80   205  12.9                                                                              92.8                                                                              81.1                                                                             6.3                                                                              6.4 6.2               5           110  4.9 1.04                                                                             4.2                                                                              0.045                                                                              81   41   12.6                                                                              92.6                                                                              77.0                                                                             6.1                                                                              9.5 7.4               6           120  4.9 1.04                                                                             3.7                                                                              0.094                                                                              81   21   12.5                                                                              92.5                                                                              74.6                                                                             6.0                                                                              11.0                                                                              8.4               7           130  4.0 1.04                                                                             3.1                                                                              0.109                                                                              80   19   10.4                                                                              91.2                                                                              70.1                                                                             6.8                                                                              12.4                                                                              10                8           140  4.9 1.04                                                                             3.0                                                                              0.125                                                                              80   20   7.6 88.4                                                                              65.3                                                                             8.6                                                                              13.6                                                                              12.5              9           145  4.9 1.04                                                                             2.5                                                                              0.185                                                                              80   18   6.2 86.1                                                                              63.0                                                                             10.1                                                                             12.8                                                                              14.               10          155  4.9 1.04                                                                             2.4                                                                              0.201                                                                              80   40   3.5 77.8                                                                              58.2                                                                             16.6                                                                             13.2                                                                              12.0              11          170  4.9 1.04                                                                             2.0                                                                              0.156                                                                              77   75   2.0 66.7                                                                              49.1                                                                             24.5                                                                             16.4                                                                              6.2               12*                                                                              L.sub.3                                                                           25   120  5.0 1.08                                                                             3.4                                                                              0.122                                                                              81   15   7.3 88.0                                                                              74.3                                                                             10.2                                                                             9.8 5.7               __________________________________________________________________________     *Solvent 2Ethylhexyl acetate                                             

                                      TABLE 15                                    __________________________________________________________________________    1-BUTENE HYDROFORMYLATION IN THE PRESENCE OF SULFONE, PHOSPHINE OXIDE,        KETO, ESTER,                                                                  HYDROXY AND ETHER SUBSTITUTED ALKYL DIPHENYL PHOSPHINE CATALYSTS              Catalyst: L.sub.3 Rh(CO)h; L/Rh = 140; Rh = 110 ppm, Precursor:               Dicarbonyl Acetylacetonato Rhodium;                                           Total Pressure 350 psi (˜26 Atm)                                         ##STR63##                                                                    R.sub.5 = CH.sub.2 CH.sub.2 CH.sub.2 OH; R.sub.6 = CH.sub.2 CH.sub.2          CH.sub.2                                                                                                                Aldehyde                                                                             Selectivities to                                                       Product                                                                              Various Com-                               Reac-                   Reac-                                                                             Linearity                                                                            pounds, %                             Example                                                                            tion          Rate Conver-                                                                            tion    100n,                                                                            Aldehydes                    Seq.*                                                                             Ligand                                                                             No. of                                                                             Temp.                                                                             H.sub.2 /CO Ratio                                                                       Constant                                                                           sion,                                                                              Time                                                                              Ratio                                                                              n + i       2-Bu-              No. LR   Complex                                                                            °C.                                                                        Initial                                                                           Feed                                                                             Final                                                                            k, Min..sup.-1                                                                     %    Min.                                                                              n/i %  n  i  Butane                                                                            tenes              __________________________________________________________________________    1   LR.sub.1                                                                           71   100 5.0 1.08                                                                             4.6                                                                              0.016                                                                              80   115 12.5                                                                              92.6                                                                             85.2                                                                             6.8                                                                              2.5 5.5                2             120 5.0 1.08                                                                             4.2                                                                              0.048                                                                              80   37  14.6                                                                              93.6                                                                             80.6                                                                             5.5                                                                              6.0 7.8                3             145 5.0 1.27                                                                             6.9                                                                              0.160                                                                              77   10  11.8                                                                              92.2                                                                             77.0                                                                             6.5                                                                              6.2 10.2               4             170 5.0 1.27                                                                             3.0                                                                              0.119                                                                              80   50  2.4 70.1                                                                             47.0                                                                             20.0                                                                             18.2                                                                              14.8               5   LR.sub.2                                                                           72   145 4.0 1.04  0.107                                                                              80   17  7.3 88.0                                                                             -- -- --  --                 6   LR.sub.3                                                                           73   120 4.9 1.08                                                                             4.2                                                                              0.060                                                                              81   34  12.6                                                                              92.6                                                                             72.8                                                                             5.8                                                                              13.1                                                                              8.3                7             145 4.9 1.08                                                                             2.5                                                                              0.267                                                                              81   7.5 7.2 87.8                                                                             74.5                                                                             10.4                                                                             6.8 8.4                8             170 4.9 1.08                                                                             2.2                                                                              0.330                                                                              79   6.0 4.0 80.0                                                                             60.8                                                                             15.2                                                                             7.4 16.6               9   LR.sub.4                                                                           74   120 4.9 1.04                                                                             4.3                                                                              0.062                                                                              80   30  11.8                                                                              92.2                                                                             78.0                                                                             6.6                                                                              8.5 6.9                10            145 4.9 1.04                                                                             3.0                                                                              0.105                                                                              80   24  6.8 87.2                                                                             67.0                                                                             9.9                                                                              12.2                                                                              11.0               11  LR.sub.5                                                                           75   120 5.0 1.08                                                                             4.5                                                                              0.040                                                                              80   28  6.1 85.8                                                                             74.2                                                                             12.3                                                                             5.8 5.7                12  (LR.sub.6).sub.2 O                                                                 76   120 5.0 1.08                                                                             3.7                                                                              0.085                                                                              80   20  9.2 90.2                                                                             73.3                                                                             8.0                                                                              11.4                                                                              7.3                __________________________________________________________________________     *Experiments of Seq. No. 1-4, 11 and 12 were carried out in 2ethylhexyl       acetate, the rest in 2propylheptyl valerate.                             

With regard to the sulfone substituted ligand, 2-ethylsulfonylethyldiphenyl phosphine, it is noted that it gave a particularly selectivecatalyst complex. The activity of this complex rapidly increased in the100° to 145° C. range. This behavior correlates with the formation of ahighly stable complex having minimum ligand exchange at 35° (Example71). The attractive catalytic properties of such a complex apparentlydepend on the specific manner of thermal activation plus stabilizationin the present process.

Hydroformylation of Various Olefinic Compounds (Examples 104-106)

In the following, the hydroformylation of various olefinic compounds isdescribed, mostly under standard conditions. As catalyst,tris-(trimethylsilylethyl diphenyl phosphine) rhodium carbonyl hydridewas used throughout these experiments. At first, the hydroformylation ofpropylene will be described. Then a series of experiments on a varietyof olefins including a non-hydrocarbon derivative will be discussed.Finally, it will be shown with isomeric pentenes, how the presentprocess could be employed when starting with a mixture of olefins.

Example 104 Hydroformylation of Propylene

The complex of Example 48 was studied at the 458 ppm rhodium level, inthe presence of a one hundred fold excess of trimethylsilylethyldiphenyl phosphine ligand, as a propylene hydroformylation catalyst. Thereaction temperature was 100° C., the 1:4 CO/H₂ pressure was 400 psi.The general procedure previously employed for butene hydroformylationwas used to carry out the reaction.

The reaction rate was found to be k=0.04 min⁻¹, expressed as thefraction reacted. In 60 minutes, 82% conversion was reached based on theCO/H₂ consumed. The ratio of n-butyraldehyde to methyl-propanal productswas 5.0. The selectivity to these aldehydes was 87.5%. The selectivityto the by-product propane was only 2.5%.

Example 105 Hydroformylation of Miscellaneous Olefinic Compounds

In a series of experiments, the results of which are summarized in Table16, a number of olefins were hydroformylated using the tris-SEP complexbased catalyst system (Seq. Nos. 1-7).

Using a high L/Rh ratio, 1-pentene was selectively hydroformylated at170° C. (Seq. No. 1). A lower L/Rh ratio was successfully used at 145°C. for the selective hydroformylation of 1-octene (Seq. No. 2).

A comparison of the n/i selectivities indicated that, in the absence ofisomerization, 1-n-olefins of increasing carbon number react withincreasing selectivity. Branching of terminal olefins further increasedn/i selectivity. This is shown by the example of 3-methylbutene (Seq.No. 4). Internal olefins could also be hydroformylated as shown in thecase of cis butene-2-hydroformylation (Seq. No. 5). It is important tonote that isomerization to 1-butene also occurred as indicated by theformation of n-valeraldehyde.

A terminal olefin having a substituent on a vinylic carbon, such as2-ethylhexene, showed an essentially specific terminal reaction toproduce only the linear aldehyde derivative (Seq. No. 6).

                                      TABLE 16                                    __________________________________________________________________________    HYDROFORMYLATION OF VARIOUS OLEFINIC COMPOUNDS IN THE PRESENCE OF SEP -       RHODIUM COMPLEX                                                               BASED CATALYST SYSTEMS                                                                 Catalyst: L.sub.3 Rh(CO)H; L = SEP = Ph.sub.2 PCH.sub.2 CH.sub.2              Si(CH.sub.3).sub.3 ; Precursor: Dicarbonyl Acetylacetonato                    Rhodium;                                                                      Total Pressure 350 psi (26 Atm)                                               Solvent: 2-Ethylhexyl Acetate                                                                     Fraction of                                                                   H.sub.2 /CO Reacted                                                                       Aldehyde                                             Reac-             Con-                                                                             Reac-                                                                             Product  Selectivities to                     Rh     tion                                                                              H.sub.2 /CO Ratio                                                                      Rate ver-                                                                             tion                                                                              Linearity                                                                              Various Compounds           Seq.                                                                             Olefinic                                                                            Conc.,                                                                            L/ Temp.                                                                             Ini-     Constant                                                                           sion                                                                             Time                                                                              Ratio                                                                             100 n, %                                                                           Aldehydes                                                                           Bu-                                                                              2-Bu-              No.                                                                              Reactant                                                                            ppm Rh °C.                                                                        tial                                                                             Feed                                                                             Final                                                                            k, min.sup.-1                                                                      %  Min.                                                                              n/i n + i                                                                              n  i  tane                                                                             tenes              __________________________________________________________________________    1  1-Pentene                                                                           105 510                                                                              170 5.0                                                                              117                                                                               3.0                                                                             0.193                                                                              80 12  7.5 88.2 53.3                                                                             7.1                                                                              19.3                                                                             20.2               2  1-Octene                                                                            113  98                                                                              145 4.0                                                                              1.04  0.257                                                                              80 8   6.8 87.2                             3            141                                                                              165 4.0                                                                              1.04  0.521                                                                              80 4   5.9 85.5                             4  3-Methyl-                                                                           110 140                                                                              145 5.0                                                                              1.27                                                                             6.6                                                                              0.274                                                                              81 10  23.9                                                                              96.0 70.8                                                                             3.0                                                                              25.2                                                                             0                     butene                                                                     5* Cis-2-                                                                              447 256                                                                              170 5.0                                                                              1.27                                                                             3.6                                                                              0.018                                                                              80 150 1.0 49.5 38.7                                                                             41.4                                                                              6.1                     Butene                                                                     6  2-Ethyl-                                                                            553  28                                                                              120  1.08                                                                            1.08                                                                             1.45                                                                             0.007                                                                              40 135 ∞                                                                           100  100                                                                              Nil                                                                              Nil                                                                              Nil                   hexene                                                                     7**                                                                              Diallyl                                                                             112 140                                                                              120 5.0                                                                              1.08                                                                             31 0.434                                                                              80 5.5 3.6 78.3                                Ether                                                                      __________________________________________________________________________     *There was a 2.6% selectivity to amyl alcohols. Both mono and                 bishydroformylated products were formed.                                 

Finally, an oxygenated diolefinic compound, diallyl ether, was alsosuccessfully hydroformylated without any apparent, major hydrogenationside reaction (Seq. No. 7). Both the mono- and bis- hydroformylatedproducts could be selectively produced. At low conversions, the primaryunsaturated aldehyde products predominated. At high conversions, a highyield of the dialdehyde products was obtained.

EXAMPLE 106 Hydroformylation of an Isomeric Mixture of Pentenes

The results of two exemplary hydroformylation experiments using a mixedpentenes feed are presented in Table 17 to show that all or certaincomponents of olefin mixtures can be reacted.

In the experiments shown therein the tris-SEP rhodium complex wasemployed in the usual manner. However, no added solvent was employed.

The data show that the 1-n-olefin component (1-pentene) was the mostreactive among the significant olefin components in both runs (Nos. 1and 2). The minor branched olefin (3-methyl butene-1) was also highlyreactive. High conversions of the internal olefin components (cis- andtrans- pentene-2's) and the olefinically substituted terminal olefin(2-methylbutene) could also be realized under the more forcingconditions of run No. 2. It is noted that under the latter conditionssome darkening of the reaction mixture occurred indicating some longterm instability.

Example 107 Continuous Hydroformylation

The tris-(trimethylsilylethyl diphenyl phosphine) rhodium, carbonylhydride catalyst system was extensively studied in a continuoushydroformylation unit.

                  TABLE 17                                                        ______________________________________                                        HYDROFORMYLATION OF MIXED PENTENES WITH                                       TRIS-(TRIMETHYLSILYLETHYL DIPHENYL                                            PHOSPHINE) RHODIUM COMPLEX CATALYST SYSTEM                                    ______________________________________                                        Catalyst: L.sup.3 Rh(CO)H, L = SEP, L/Rh, 139; Precursor:                     Dicarbonyl Acetylacetonato Rhodium;                                           Olefin: 100 g Mixed Pentenes with Added Solvent                                                  Reaction Conditions                                        Number       O: Feed     1        2                                           ______________________________________                                        Temperature, °C.  120      120-145                                     Time, Min.               300      360                                         Olefin Conversion, %      30       55                                         Rh Conc. ppm             109      293                                         ______________________________________                                                  Composition of Reaction Mixture                                                 Mole   Mole                                                       C.sub.5 Hydrocarbons                                                                      %      %      Conv. %                                                                              Mole % Conv. %                               ______________________________________                                        3-Methylbutene                                                                            0.31   0      100    0      100                                   i-Pentane   0.45   0.53   --     1.02   --                                    l-Pentane   8.04   0.89   89     0.71   91                                    2-Methylbutene                                                                            24.61  19.13  22     7.14   71                                    n-Pentene   4.14   5.10   --     6.10   --                                    t-2-Pentene 28.97  19.95  31     5.63   81                                    c-2-Pentene 12.32  7.35   40     2.19   82                                    2-Methylbutene-2                                                                          21.04  22.22   0     22.46   0                                    ______________________________________                                        Aldehydes  None        Mole %   Mole %                                        ______________________________________                                        2-methylpentanal                                                                         --          13.86    27.33                                         3-methylpentanal                                                                         --          5.69     16.97                                         4-methylpentanal                                                                         --          --       --                                            n-hexanal  --          5.27     10.46                                         ______________________________________                                    

The feed was butene-1 and the products were continuously removedtogether with the unreacted volatile components of the reaction mixture.The typical reaction temperature for the SEP based system was 120° C.Comparative runs were also carried out with a similar TPP based systemat 100° C. Both systems could be successfully operated on the short run,although it appeared that the known degradation reactions and thestripping of the valeraldehyde trimer by-product at 100° C. could becomea problem with TPP. The SEP system showed excellent long term stabilityand activity maintenance.

A representative 30 day continuous operation of the SEP catalyst systemis illustrated in FIG. 12. With regard to the continuous operatingconditions, it is noted that the total synthesis gas pressure was lower(125 psi, ˜8.5 Atm) and the H₂ /CO ratio higher (10/1) than in most ofthe batch studies. Also a higher concentration of rhodium (270 ppm) anda higher L/Rh ratio (210) were employed. Under these conditions a batchexperiment produced results similar to those found in the continuousoperation.

In the continuous hydroformylation the catalyst was generated fromdicarbonyl acetylacetonato rhodium in situ. The precursor was a moreactive but much less selective hydroformylation catalyst than thedesired final catalyst.

In a typical operation 1-butene was introduced into the reactor at arate of 4.4 mole per hour. The rate of CO was typically 2 standard cubicfeet per hour (SCFH). The hydrogen was introduced int he 15 to 25 SCFHrange. By changing the hydrogen ratio the aldehyde production rate andother parameters could be appropriately and reversibly controlled.

During the reaction isomeric valeraldehyde trimers and some tetramerswere formed. At an equilibrium concentration they were in theconcentration range of from about 50 to 80% by wt.

After the reaction system came to equilibrium, the rate of hydrogen gelfeed introduction was decreased from 19.2 to 17.6 SCFH (1 SCFH=28.3 dm³/hr) during the seventh day of the run. This resulted in an increasedproduction rate. As expected, this process was fully reversible. Also, adecrease of the synthesis gas feed rate above the initial level, to 24.5SCFH on the 15th day, resulted in the expected decreased productionrate.

On the nineteenth day, the reaction temperature was raised to 125°. Thisresulted in an about 39% reaction rate increase as expected on the basisof an activation energy of 15.5 kcal. Subsequent changes of the spacevelocity of the synthesis gas feed at this higher temperature resultedin the expected reaction rate changes.

On the basis of the kinetic changes observed during the approximately 3weeks of operation shown by the figure and on the basis of othercontinuous hydroformylations with the same catalyst system, a rateequation was developed. This rate equation did fit all the data. Therate constant remained unchanged after the startup equilibrium periodfor the 25 days shown. It is noted that the lack of change of the rateconstant means that there is no loss of catalyst activity during thisperiod. The only long term change in the catalyst system was someoxidation, probably by oxygen, of the phosphine ligand to thecorresponding phosphine oxide. In the presence of excess phosphine, thisoxidation had no adverse effect on the reaction rate. Combined gaschromatography and mass spectroscopy studies could not show any evidenceof a ligand degradation similar to that reported to occur viao-phenylation in the TPP system.

Combined Hydroformylation-Aldolization Examples (108-111) Example 108Combined Hydroformylation-Aldolization of 1-Butene at 120° C. in thePresence of tris-(Trimethylsilylethyl Diphenyl Phosphine) [SEP] RhodiumCarbonyl Hydride Complex ##STR64##

The combined hydroformylation, aldolization and hydrogenation ofbutene-1 was studied under typical conditions of the presenthydroformylation process. The DTS rhodium complex was utilized as atypical substituted alkyl diaryl phosphine rhodium complex catalyst forhydroformylation and hydrogenation. Potassium hydroxide inmethoxytriglycol was employed as an aldolization catalyst. Themethoxytriglycol was also used as the solvent for the other componentsof the mixture. The catalyst system was employed at the 110 ppm rhodiumconcentration level. The ligand to rhodium ratio was 140. The 1-butenereactant was employed in a standard manner. The initial H₂ /CO mixtureused to pressure the mixture to 350 psi (26 atm.) had a 5/1 mole ratio.The feed gas to maintain this pressure was a 1.5 to 1 mixture. Thelatter ratio was employed because it is theoretically needed to producethe n,n- and i/n-anals.

The reaction and product parameters of a group of experiments designedto observe the effect of varying concentrations of KOH are summarized inTable 18. The product parameters, i.e., selectivities to the variousproducts were obtained by glc analyses. For the analyses of the C₅ andC₁₀ aldehydes, a special 2 m Carbowax column 10% CW on Chromosorb Pdiatomaceous earth was used. This was provided by Supelco, Inc., SupelcoPark, PA. It provided good separation of the n,n-enal from the n,n-anal.

                                      TABLE 18                                    __________________________________________________________________________    COMBINED HYDROFORMYLATION-ALDOLIZATION OF 1-BUTENE AT 120° C. and      350 psi                                                                       (2 atm.) in the Presence of SEP Rhodium Complex and Varying Amounts of        KOH                                                                                         SEP = L = Ph.sub.2 CH.sub.2 CH.sub.2 Si(CH.sub.3).sub.3 ;                     L/Rh = 140; Rh = 110                                                             Fraction of   Approx. Selectivities                                           H2/CO Reacted to Aldehydes                                                    Rate Con-                                                                              Reaction                                                                           Mole %          % n,                                                                              Selectivity                Seq.                                                                             KOH H2/CO Ratio                                                                             Constant                                                                           version                                                                           Time C5's n,n (i)-                                                                          n,n-                                                                             n/i 100 n                                                                             to n-Butane                No.                                                                              %   Initial                                                                           Feed                                                                             Final                                                                            k, min.sup.-1                                                                      %   Min. i n  anal                                                                              enal                                                                             Ratio                                                                             n + 1                                                                             mole                       __________________________________________________________________________                                                       %                          1  Nil 5   1.08                                                                             2.7                                                                              0.056                                                                              80  50   9.2                                                                             90.8       9.9    14.0                       2  Nil 5   1.5                                                                              24.1                                                                             0.051                                                                              80  42   3.1                                                                             96.9      32.1                                                                              96.9                                                                              18.8                       3  Nil 5   1.5                                                                              26.8                                                                             0.05 15   4   3.3                                                                             96.7      29.1                                                                              96.7                           2  Nil 5   1.50                                                                             21.3                                                                             0.042                                                                              15   6   6.7                                                                             93.3      13.8                                                     45  15   5.8                                                                             94.2      16.3                                                     60  24   5.5                                                                             94.5      17.2                                                     80  80   6.2                                                                             93.8      15.0                                                                              93.8                                                                              17.7                       3  0.05                                                                              5   1.50                                                                             47 0.059                                                                              80  34   4.1                                                                             47.5                                                                              8.4                                                                              40.0                                                                             34.9                                                                              97.2                                                                              28.9                       4  0.05                                                                              5   1.50                                                                             17.7                                                                             0.061                                                                              15   4   6.1                                                                             81.6                                                                              0.8                                                                              11.7                                                                             17.6                                                                              94.6                                                 30  18   5.5                                                                             76.8                                                                              1.0                                                                              16.7                                                                             20.5                                                                              95.4                                                 45  11   5.4                                                                             72.9                                                                              1.5                                                                              20.2                                                                             21.6                                                                              95.6                                                 60  16   5.2                                                                             67.3                                                                              2.7                                                                              24.7                                                                             23.5                                                                              95.9                                                 80  30   5.9                                                                             51.5                                                                              7.8                                                                              34.8                                                                             23.2                                                                              95.9                                                                              17.7                       5  0.10                                                                              5   1.17                                                                             6.52                                                                             0.062                                                                              15   5   2.9                                                                             17.8                                                                              3.0                                                                              50.2                                                                             42.9                                                                              94.3                                                 80  32   9.3                                                                             34.1                                                                             13.0                                                                              43.6                                                                             15.8                                                                              77.1                                                                              15.0                       6  0.10                                                                              5   1.50                                                                             5.0                                                                              0.048                                                                              80  42   3.4                                                                             27.1                                                                             18.3                                                                              51.2                                                                             49.2                                                                              98.0                                                                              31.3                       7  0.20                                                                              5   1.50                                                                             5.0                                                                              0.043                                                                              80  40   2.9                                                                             16.0                                                                             16.0                                                                              65.2                                                                             60.5                                                                              98.4                                                                              28.8                       8  0.20                                                                              5   1.50                                                                             13.6                                                                             0.049                                                                              15   3   --                                                                              -- 10.8                                                                              89.2   --                                              0.028                                                                              30   5   3.7                                                                             -- 11.5                                                                              84.9                                                                             50.6                                                                              98.0                                                 45  12   3.0                                                                             -- 12.0                                                                              85.0                                                                             64.4                                                                              98.5                                                 60  16   3.3                                                                              7.5                                                                             13.6                                                                              75.8                                                                             57.1                                                                              98.3                                                 80  32   3.6                                                                             17.7                                                                             18.6                                                                              60.1                                                                             48.0                                                                              98.0                                                 92  62   4.9                                                                             14.1                                                                             34.5                                                                              46.5                                                                             35.9                                                                              97.3                                                                              16.0                       __________________________________________________________________________     However, the separation of the n,n-enal from the i,n-enal was not good.     The small quantities of the i,n-enal formed could not be determined.     Therefore, the overall n,i-ratios in the reaction mixtures with KOH could     not be exactly determined. The aldehyde selectivity to the main final     C.sub.10 aldehyde product, the n,n-enal, also includes minor quantities of     the i,n-anal. However, this inclusion causes less than 10% change in the     composition, since the minor i-C.sub.5 aldehyde is crossaldolized at a     very slow rate. The glc percentages are indicated on the basis of the peak     intensities. No corrections were made for the possibly different glc     response to C.sub.5 and C.sub.10 compounds.

In the first four experiments, the hydroformylation of butene wasstudied in methoxytriglycol but in the absence of KOH aldolizationcatalyst (Seq. Nos. 1 to 4) for comparison. All three experimentsstarted with 5/1 H₂ CO gas. In the first experiment, the H₂ /CO ratio ofthe feed gas was close to one as usual. This experiment gave the usualhigh n/i ratio of C₅ aldehydes. This indicated that the solvent is anadvantageous one, comparable to other polar oxygenated solvents (Seq.No. 1).

The rest of the experiments used the same initial H₂ /CO ratio of 5 buta different H₂ /CO feed, of 1.5. Also, the contents of the third andfourth reaction mixture were sampled for comparison with the experimentsusing added KOH. This and the other sampled runs provided less reliableabsolute values than the uninterrupted experiments. However, sequencesgave comparative relative numbers which showed the change of selectivitywith increasing conversion.

The second experiment (Seq. No. 2) showed a much increased n/i ratiocompared to the first. This was the consequence of the increasing H₂ /COratio, i.e., decreasing CO partial pressure during the reaction. Due todecreased availability of CO, this run also resulted in morehydrogenation of the 1-butene starting material and isomerized 2-butenesto n-butane.

The results of the first sampled experiment are somewhat similar. Thisexperiment shows that as a consequence of increasing H₂ /CO ratio, theselectivity is much higher at 80% conversion. (Seq. No. 3).

The fourth experiment (Seq. No. 4) was sampled four times during therun. It showed that up to 60% conversion, the n/i ratio was moderatelyincreasing as an apparent consequence of the increasing H₂ /CO ratio inthe reaction mixture.

The second group of experiments (Seq. Nos. 5-10) was run using varyingamounts of KOH, in the 0.05 to 0.2% range, under the same conditions.The data indicated that 0.2% KOH was sufficient for the rapid conversionof the primary n-C₅ aldehyde product (Seq. Nos. 7 and 8). Thealdolization rate was much slower when 0.05% KOH was used (Seq. Nos. 5and 6). The rate of the hydroformylation was estimated on the basis ofthe measured rate of synthesis gas consumption. Increasing H₂ /CO ratiosgenerally resulted in increased n/i ratios and increased percentages ofn-butane formation. Due to apparent CO starvation, the non-sampledmixtures gave rise to significantly higher H₂ /CO ratios than thosefrequently sampled during the run.

The hydrogenation of the unsaturated aldehyde to the saturated aldehydewas relatively low. At 45% synthesis gas conversion, the percentagen,n-anal formed was less than 10% of the n,n-enal present. At thatconversion, the overall selectivity to the n,n-enal was in excess of80%.

Example 109 Sequential Hydroformylation, Aldolization, Hydrogenation inSeparate Steps

In a series of experiments, n-valeraldehyde was produced by thehydroformylation of 1-butane and separated from the i-isomer. A 20%methoxytriglycol solution of the n-valeraldehyde was then aldolized toprovide the n,n-enal condensation product. It was observed that thealdolization was much slower in the absence of the hydroformylationcatalyst system than in the presence of it in the previous example.After 30 minutes reaction time, only a 1.2% conversion was reached.After 14 hours, the aldehye conversion was 47.2%, i.e., theconcentration of the n,n-enal in mole equivalents was 47.2%.

During the above experiment, and other experiments with KOH solutions inmethoxytriglycol, yellow, then amber, then brown color formation wasobserved, indicating potential instability. The addition of 2% KOH tomethoxytriglycol resulted in an amber color even at room temperature.Therefore, the amount of KOH in the hydroformylation experiments wasminimized.

to the reaction mixture from the above aldolization experiment, thehydroformylation catalyst of the previous example was added. Then themixture was pressured to 570 psi (˜39 atm.) and heated as usual to 120°C. with a 20/1 mixture of H₂ /CO. A high H₂ /CO ratio was used increasethe hydrogenation rate of the n,n-enal to the n,n-anal.

The hydrogenation of the n,n-enal to the n,n-anal was followed by glc.During the first 90 minutes, the percentage conversion increased asfollows: 6 (5 min.); 13 (20 min.); 21 (40 min.); 28 (60 min.); and 39(90 min.). Under these conditions, no further significant aldolizationof the n-C₅ aldehyde occurred.

Example 110 Combined Hydroformylation-Aldolization of 1-Butene withVarious Tris-(Alkyl Diphenyl Phosphine) Rhodium Carbonyl HydrideComplexes

The combined hydroformylation aldolization of 1-butene under theconditions of Example 108 was also studied witht he tris-(n-butyldiphenyl phosphine) and the tris-(n-hexyl diphenyl phosphone) complexes.The SEP complex was also used in this group of experiments under similarconditions but using a 1/1 rather than a 5/1 initial H₂ /CO reactantratio. The results are shown in Table 19.

Overall, the data of Table 19 show that different alkyl diphenylphosphine complexes are similar catalysts for combined hydroformylationaldolization. The results also indicate that the provision of sufficientcarbon monoxide for hydroformylation is a key factor in avoiding olefinhydrogenation.

The first two experiments (Seq. No.s 1 and 2) with the butyl diphenylphosphine complex (A) show the effect of the KOH on the aldolization.The results are similar to those obtained in comparative experimentsusing the SEP complex in a previous example (See Table 19). The secondpair of experiments (Seq. Nos. 3 and 4) shows the effect of startingwitha synthesis gas having a low, i.e., 1.5, H₂ CO ratio. Lowerselectivities to the n-product are obtained but the reaction rates areincreased and the by-product n-butane formation is drastically reduced.The two different catalyst ligands used in these experiments, i.e.,n-hexyl diphenyl phosphine (B) and trimethylsilylethyl phosphine (C),led to similar results.

Example 111 Combined Hydrogenation-Aldolization of 1-Butene at 145° C.in the Presence of tris-SEP and tris-TPP Rhodium Carbonyl HydrideComplexes

                                      TABLE 19                                    __________________________________________________________________________    COMBINED HYDROFORMYLATION ALDOLIZATION OF 1-BUTENE AT 120° C. IN       THE PRESENCE OF VARIOUS                                                       TRIS-(ALKYL DIPHENYL PHOSPHINE) RHODIUM CARBONYL HYDRIDE COMPLEXES            L = Ar.sub.2 PR; A: R = C.sub.4 H.sub.9 ; B: R = C.sub.6 H.sub.9 ; C: R =     CH.sub.2 CH.sub.2 Si(CH.sub.3).sub.3 ; L/Rh = 140; Rh = 110 ppm;              Pressure = 350 psi (26 Atm)                                                                                       Approximate Selectivities                                      Fraction       to Aldehydes          Select-                                  H.sub.2 /CO Reacted                                                                      Reac-                                                                             Mole %                ivity                                    Rate       tion      C10's      % n  to n-                No.Seq.                                                                          SpeciesLigand                                                                     %KOH                                                                              InitialFeedFinalH.sub.2 /CO Ratio                                                       k, min.sup.-1Constant                                                              sion %Conver-                                                                       Min.Time                                                                          i-nC5's                                                                             analn,n(i)                                                                        enaln,n-                                                                         Ration/i                                                                          ##STR65##                                                                          mole               __________________________________________________________________________                                                              %Butane             1  A   Nil 5   1.5                                                                              20.1                                                                             0.058                                                                              15    4   4.9                                                                              95.1      19.6                                                                              95.1                                               80    34  4.4                                                                              95.6      21.9                                                                              95.6 13.0                2  A   0.1 5   1.5                                                                              21.0                                                                             0.043                                                                              15    5   10.7                                                                             16.8                                                                             7.3 65.2                                                                             15.1                                                                              93.8                                               80    42  6.7                                                                              24.5                                                                             21.9                                                                              46.9                                                                             24.1                                                                              96.0 13.7                3  B   0.1 1.5 1.5                                                                              11.6                                                                             0.151                                                                              15    2   18.5                                                                             75.2   7.3                                                                              4.8 82.8                                               80    12  14.1                                                                             63.1                                                                             6.7 16.0                                                                             7.7 88.5 1.9                 4  C   0.1 1.5 1.5                                                                              6.8                                                                              0.088                                                                              15    3   18.0                                                                             75.7   6.3                                                                              4.9 83.1                                               80    20  16.0                                                                             73.6                                                                             0.9 9.5                                                                              5.9 88.5                                               109   120 19.0                                                                             12.8                                                                             34.4                                                                              33.8                                                                             7.5 88.2 2.1                 __________________________________________________________________________

The combined hydroformylation-aldolization of 1-butene was also studiedunder similar conditions at 145° C. At this temperature, the knowntris-TPP complex is unstable under the reaction conditons. In contrast,the novel tris-SEP complex is stable. The experimental conditions andresults are shown in Table 20.

As it is shown in this table, in the first pair of experiments (Seq.Nos. 1 and 2), both the triphenyl phosphine (TPP) complex and thetrimethylsilylethyl diphenyl phosphine (SEP) complex were employed ashydroformylation catalysts in methoxytriglycol in the absence of KOH. Acomparison of the results showed that the rate of the SEP complexcatalyzed reaction was higher. Even more significantly, the selectivityof the SEP complex to produce aldehydes of high n/i ratios was muchhigher (Seq. No. 1). At 80% conversion, the SEP catalyzed reaction had a7.6 n/i ratio. The comparable ratio for the TPP system was 3.1 (Seq. No.2). Most revealingly, the TPP reaction gave an n/i ratio of 12.4 at 15%conversion. Apparently, during the further course of the experiment, theTPP catalyst system decomposed and led to species of much lowercatalytic activity and selectivity.

In the second pair of experiments (Seq. Nos. 3 and 4), the same twocatalyst systems were employed in the presence of KOH to effecthydroformylation and aldolization. KOH was found to be an effectivealdolization catalyst. Both complexes were also effective in catalyzingthe hydrogenation of the aldol condensation products. However, thedifference between the activity and selectivity of the two catalystsremained. The SEP complex plus KOH system produced a 6.6 n/i ratio ofaldehydes at 80% conversion (Seq. No. 3). The comparative n/i ratio forthe TPP complex plus base was only 4.2 (Seq. No. 4).

                                      TABLE 20                                    __________________________________________________________________________    COMBINED HYDROFORMYLATION ALDOLIZATION OF 1-BUTENE AT 145° C. AND      350 psi (˜26 atm.) IN THE                                               PRESENCE OF TRIS-SEP AND TRIS-TPP RHODIUM CARBONYL HYDRIDE COMPLEXES          SEP = Ph.sub.2 PCH.sub.2 CH.sub.2 CH.sub.2 Si(CH.sub.3).sub.3 ; TPP =         Ph.sub.3 P; L/Rh = 140; Rh = 110 ppm                                                                              Approximate Selectivities                                      Fraction       to Aldehydes          Select-                                  H.sub.2 /CO Reacted                                                                      Reac-                                                                             Mole %                ivity                                    Rate       tion      C10's      % n  to n-                No.Seq.                                                                          SpeciesLigand                                                                     %KOH                                                                              InitialFeedFinalH.sub.2 /CO Ratio                                                       k, min.sup.-1Contant                                                               sion %Conver-                                                                       Min.Time                                                                          i-n C5's                                                                            analn,n(i)                                                                        enaln,n-                                                                         Ration/i                                                                          ##STR66##                                                                          mole               __________________________________________________________________________                                                              %Butane             1  SEP Nil 5   1.17                                                                             2.7                                                                              0.174                                                                              79    18  11.6                                                                             88.4      7.6 88.6 12.0                2  TPP Nil 5   1.5                                                                              14.7                                                                             0.138                                                                              15    1   7.5                                                                              92.5      12.4                                                                              92.5                                               80    90  24.6                                                                             75.4      3.1 75.4 15.4                3  SEP 0.2 5   1.5                                                                              4.6                                                                              0.07 80    42  15.2                                                                             21.1                                                                             44.4                                                                              19.4                                                                             6.7 87.0 19.4                4  TPP 0.1 5   1.5                                                                              6.4                                                                              0.121                                                                              15    1.5 8.6                                                                              38.4                                                                             3.0 50.0                                                                             16.8                                                                              94.4                                               80    80  29.7                                                                             12.0                                                                             48.5                                                                              9.8                                                                              4.2 80.6 13.2                __________________________________________________________________________

The above quantitative observations on the relative stability of the SEPand TPP based systems could be qualitatively predicted when observingthe respective reaction mixtures after the reactions. The SEP systemswithout and with base were yellow and amber, respectively. The TPPsystems with and without base became black.

INDUSTRIAL APPLICABILITY

The catalysts and processes of the invention are useful in producingaldehydes from olefins.

What is claimed is:
 1. A nitrogen heterocycle substituted alkyl diarylphosphine rhodium carbonyl hydride complex catalyst of the formula##STR67## wherein Ar is an aryl group containing from 6 to 10 carbonatoms;Q is a divalent organic radical selected from an alkylene radicaland an alkylene radical the carbon chain of which is interrupted atleast one ether oxygen or phenylene group wherein said alkylene radicalcontains from 1 to 30 carbon atoms; R represents a divalent organicradical selected from the group consisting of ##STR68## which togetherwith the nitrogen atom forms a heterocyclic nitrogen-containing ringwherein R⁴, R⁵, R⁶, R⁷ and R⁸ are hydrocarbyl radicals such that saidheterocyclic ring contains from 5 to 6 atoms; and g is 2 or
 3. 2. Acatalyst complex of claim 1 wherein Ar is phenyl and Q is (CH₂)₂ or(CH₂)₃.
 3. A catalyst complex according to claim 1 of the formula##STR69## wherein Ph is phenyl and m is 1 to
 30. 4. A catalyst complexof the formula ##STR70## wherein Ph is phenyl.
 5. A catalyst complex ofthe formula ##STR71## wherein Ph is phenyl.
 6. A heterocycle-substitutedalkyl diaryl phosphine rhodium carbonyl hydride complex catalyst of theformula ##STR72## wherein Ar is an aryl group containing from 6 to 10carbon atoms;Q is a divalent organic radical selected from an alkyleneradical the carbon chain of which is interrupted with at least one etheroxygen or phenylene group, wherein said alkylene radical contains from 1to 30 carbon atoms; and E is a member selected from --N< and R is anorganic radical which when bonded to --E R forms a heterocyclic radicalsaid heterocyclic radical being selected from the group consisting of##STR73## pyrryl, and furyl and wherein R⁴, R⁵, R⁶, R⁷ and R⁸ arehydrocarbyl radicals such that said heterocyclic ring contains 5 to 6atoms.
 7. The complex catalyst of claim 6 wherein Ar is phenyl and Q is(CH₂)₂ or (CH₂)₃.
 8. A heterocycle-substituted alkyl diaryl phosphinerhodium carbonyl hydride complex catalyst of the formula

    (Ar.sub.2 PQY).sub.3 Rh(CO)H

wherein Ar is an aryl group containing from 6 to 10 carbon atoms; Q is adivalent organic radical selected from an alkylene radical the carbonchain of which is interrupted with at least one ether oxygen orphenylene group, wherein said alkylene radical contains from 1 to 30carbon atoms; and Y is a heterocyclic aryl group selected from the groupconsisting of pyrryl and furyl.
 9. Tris(pyridylethyl diphenyl phosphine)rhodium carbonyl hydride.
 10. Tris(furylethyl diphenyl phosphine)rhodium carbonyl hydride.
 11. Tris(carbazylethyl diphenyl phosphine)rhodium carbonyl hydride.